(navigation image)
Home American Libraries | Canadian Libraries | Universal Library | Community Texts | Project Gutenberg | Children's Library | Biodiversity Heritage Library | Additional Collections
Search: Advanced Search
Anonymous User (login or join us)
Upload
See other formats

Full text of "Conference proceedings : technology transfer conference no. 1/"

[;: 



W,N!;;rRY iii THE tNViHONMfrJj I 



^ ^ u[nc:; ^__ _J 



CONFERENCE PROCEEDINGS 



iECHNOLOGY TRANSFER CONFERENCE NO. 1 



Skyline Hotel, Toronto, Ontario 
November 25, 1980 



RESEARCH ADVISORY COMMITTEE 

Ministry of the Environment 

Province of Ontario 



The Honourable 
Keith C. Norton, Q.C., 
Ministry Minister 

O^the Graham W. S. Scott, Q.C., 

Environment Deputy Minister 

Ontario 







CONFERENCE PROCEEDINGS 

TECHNOLOGY TRANSFER CONFERENCE NO. 1 

Skyline Hotel, Toronto, Ontario 
November 25, 1980 

RESEARCH ADVISORY COMMITTEE 

Ministry of the Ervironment 

Province of Ontario 




Ontario 



Ministry 
of the 
Environment 



The Honourable 

Harry C. Parrott, DDS 

Minister 

Graham W. S. Scott, QC 
Deputy Minister 



Copyright Provisions and Restrictions on Copying: 

This Ontario Ministry of the Environment work is protected by Crown 
copyright (unless otherwise indicated), which is held by the Queen's Printer 
for Ontario, It may be reproduced for non-commercial purposes if credit is 
given and Crown copyright is acknowledged. 

It may not be reproduced, in all or in part, part, for any commercial purpose 
except under a licence from the Queen's Printer for Ontario. 

For information on reproducing Government of Ontario works, please 
contact Service Ontario Publications at copvright@ontario.ca 



TABLE OF CONTENTS 



Title of Paper 

Environmental Effects of 
Waste Oil as a Road Dust 
Suppressant 



Speaker 

F. Guillaume 



Affiliation 

L. S. Love and 
Associates Canada Ltd. 
158 Kennedy Road, South 
Brampton, Ontario 
L6W 3G7 



Page 



The Effects of Road Oiling 
on PCB Accumulation in 
Aquatic Life 

Waste Oil Utilization 

Bio-accumulation Rates, 
Acute and Chronic Effects 
of New Dielectric Fluid 
Products on Fish 

Factors Affecting the 
Accumulation of Organics 
in Fish 

The Problem of Abandoned 
Mines in Ontario - A 
Confrontation with History 

Methodology for Developing 
a Quantity and Location 
Inventory of Hazardous 
Compounds in Ontario 



Ontario's Seven Point 
Program for Liquid Indus- 
trial Waste Disposal 

Environmental Impairment 
Liability Insurance 



Subsurface Contaminant 
Migration from Landfills - 
Research Results 



Organic Contaminant Removal 
in Drinking Water - An 
Overview 



K. Suns 

E. W. Turner 
G. W. Ozburn 



G. R. Craig 



J. E. Duignan 



K. R. Ashwood 



P. Isles 



G.T.G. Scott 



J. A. Cherry 



K. J. Roberts 



Water Resources Branch 19 



Waste Management Branch 37 

Lakehead University 
Department of Biology 
Thunder Bay, Ontario 
P7B 5E1 A9 

Water Resources Branch 92 



Waste Management Branch 94 



Acres Consulting 

Services Ltd. 

5259 Dorchester Road 

Niagara Falls, Ontario 

L2E 6W1 113 

Waste Management Branch 12A 



Geoffrey T. G. Scott 

Consulting Engineer 

Suite 201 

801 York Mills Road 

Don Mills, Ontario 

M3B 1X7 146 

University of Waterloo 
Faculty of Science 
Waterloo, Ontario 
N2L 3G1 155 

Pollution Control 

Branch 175 



Organic Contaminant Removal 
in Drinking Water - Field 
Experiences 



R. B. Hunsinger 



Pollution Control Branch 198 



Table of Contents (cont'd.) 

Title of Paper Speaker 

Viruses and the Environment G. Jenkins 



Affiliation Page 

Laboratory Services 

Branch 212 



An Application of Thermal 
Sensing Techniques 



W. Bernert 



The Pickering "A" Thermal 
Plume During Winter Months. 
Some Preliminary Results 
from a Co-operative Study 

The Uptake of Methyl- 
mercury by Walleye through 
a Simulated Ecosystem as 
a Function of Selected pH 
Regimes 

Atmospheric Deposition of 
Mercury in Ontario 



R. R. Weller 



T. A. Watson 



N. D. Johnson 



Intertech Remote 
Sensing Ltd. 
P.O. Box 507, R.R. #5 
Hunt Club Road 
Ottawa, Ontario 
KIG 3N3 

Water Resources Branch 



J. F. MacLaren Ltd. 
1220 Sheppard Avenue E, 
Suite 100 

Willowdale, Ontario 
M2K 2T8 

Ontario Research 

Foundation 

Sheridan Park Research 

Community 

Mississauga, Ontario 

L5K 1B3 



234 
243 



264 



297 



Event Precipitation Samplers D. M. Kane 

or Use in Acid Rain 

Studies 



Definition of the Sphere of E. Nieboer 

Influence of the Mining 

Activities at Elliot Lake, 

Ontario by Assessment of 

the Levels of Uranium and 

Other Elements in Lichens 

and Mosses 

Acid Rain - An Overview of E. W. Piche 
the Ontario Program 



United Technology and 
Science Inc. 
75 Eglinton Avenue E. 
Toronto, Ontario 
M4P 1H3 

McMaster University 
Department of Bio- 
chemistry Health 
Sciences Centre 
1200 Main Street W. 
Hamilton, Ontario 
L8S 4J9 

Ministry of the 
Environment 



322 



343 



366 



INTRODUCTION 



Ministry of the Environment 
Province of Ontario 

Technology Transfer Conference No. 1 
Tuesday, November 25, 1980 

Skyline Hotel 
655 Dixon Road 
Rexdale, Toronto 
Ontario M9W 1J4 

Featuring Completed Research Projects 
Supported by tlie Provincial Lottery 
Trust Fund 

Sponsored and presented by the 
Research Advisory Committee 
Ministry of the Environment 



The Research Advisory Committee, Ontario Ministry of the Environment 
sponsored Technology Transfer Conference No. 1 on November 25, 1980 
at the Skyline Hotel for the purpose of distributing information 
arising from Provincial Lottery Research Projects and from other 
selected M.O.E. in-house and external research projects. At this 
conference. Contractors, Principal Investigators, Liaison Officers 
and Researchers described and discussed results of their projects 
giving emphasis to useful applications of the investigational work. 

The attendance at this one day session was divided between two 
parallel sessions of their choice. The program was structured 
for M.O.E. Staff and Researchers, Ontario a-^d Federal Government 
Personnel, Consultants, Contractors, University Personnel, Industry 
Representatives and Media. 

Twenty papers were given at the Conference and of these, thirteen 
were supported with Provincial Lottery Trust Funds. 



ACKNOWLEDGEMENT 

This Conference Proceedings is issued to describe environmental 
oriented research projects conducted by the Ontario Government, 
assisted by the Federal Government, Ontario Hydro, National Water 
Research Institute, Universities and the Private Sector. All 
initial enquiries regarding the papers given at the Conference 
should be made to the authors and speakers or to their affiliation. 

DISCLAIMER 

The contents of this Conference Proceedings have been reviewed by the 
Research Advisory Committee and approved for publication. Approval 
does not signify that the contents necessarily reflect the views and 
policies of the Ontario Ministry of the Environment, nor does ment-'on 
of trade names or commercial products constitute endorsement or 
recommendation for use. 

Session Chairmen at Conference No. 1: 



D. A. McTavish, 

B. I. Boyko, 

P. D. Foley. 

G . C . Ronan , 



Southwestern Region 
Waste Management Branch 
Pollution Control Branch 
Laboratory Services Branch 



"ENVIRONMENTAL EFFECTS OF WASTE 
OIL AS A ROAD DUST SUPPRESSANT"., 



by 

F. Guillaume 

L.S. Love and Associates Canada Ltd 
Brampton, Ontario. 



FOR PRESENTATION AT THE 
TECHNOLOGY TRANSFER CONFERENCE NO.l 



November 25, 1980. 

Skyline Hotel , 
Rexdale, Ontario, 



1. INTRODUCTION: 

This paper will give a brief overview of a two-year study programme on the 
environmental effects of waste oil as a road dust suppressant. Detailed 
reports were prepared for presentation to the M.O.E. Waste Management 
Branch, after completion of the respective phases of the study. 

The unsolicited proposal described the purpose of the study programme as 
follows: "To define the transport of oil and some of its components into 
the immediate environment of the road, i.e. dust, soil, vegetation and 
water, relative to an untreated section of road and a section which was 
treated with calcium chloride". 

The potential difficulty of assessing the environmental effects was recognized, 
especially when these effects might be taken to include any adverse effects 
on wildlife, cattle, crops and humans. Clearly, a much broader study 
programne over an extended time period would be needed to attempt to 
evaluate those effects. 

In our opinion a 1-year but preferably a two-year field study could provide 
some, if not most of the Information required per the stated purpose for 
this study programne. 

This study was undertaken by our Company on behalf of the Ministry of the 
Environment (MOE) and in conjunction with the Ministry of Transportation 
and Conmuni cations (MTC) who evaluated the physical characteristics of the 
treated roads and the observed effectiveness of dust control using the 
several dust suppressants. 

During the summer and fall of 1977, four test roads were used in this study 
in Haldimand Township, Northumberland County, Ontario. During the 1978 
phase two of these test roads were used again, while a third road was 
sampled only, without having been retreated with dust suppressants. During 
1978 the sampling continued from mid-May to mid-November. 



1. 



INTRODUCTION, (cont'd) 



A key factor in the successful completion of all field activities during 
the study programme was the excellent co-operation we received from Mr. 
Tom McBride, Superintendent of Roads, Haldimand Township, in the selection 
and preparation of the test roads and his willing assistance throughout 
the 2-yedr study. 

2- PROCEDURES AND METHODS: 

The location of the four selected test roads in Haldimand Township is 
shown in Fig. No. 1. Road 1 was in east-west direction whereas roads 2. 
3 and 4 were in a north-south position, so that the effect of wind direction 
on dust dispersion could be evaluated. 

As shown in Fig. i, both roads 1 and 2 crossed two small streams each, to 
permit an evaluation of any effects on nearby streams due to the dust 
suppressants. 

The test roads had to be previously untreated gravel roads, approximately 
1.6 km long, divided roughly into one third sections with the middle 
section as control separating the two treated sections, one with waste oil 
and the other with calcium chloride. 

During the sampling programmes the Township Roads Superintendent had agreed 
to curtail the routine grading and maintenance of the test roads except for 
emergency attention as required, to correct severe potholing that had 
'developed. 

Proper selection of the test roads had to provide for adjacent shoulders 
and field areas suitable for soil sampling within a distance of 25 m from 
the road edge and also sufficient quantities of suitable types of vegetation 
in the shoulder areas. 

For the 1978 phase of the study, roads 1 and 4 were selected for retreatment 
at the same sections as used in 1977. and a similar sampling programme was 
continued with the exception of vegetation and field soil. Road 3 was not 
retreated but was kept as a long term control with only road bed samples being 
taken on a once monthly basis. 



g. PROCEDURES AND METHODS, (cont'd) : 

Application of waste oil for road dust control is usually in the range of 

2 2 

1-1.6 1/m to an upper limit of 2.7 1/m . This is equivalent to a range 

of 0.2-0.29 Igal/Yd^ and a limit of 0.5 Igal/Yd^. The actual application 

p 
rates during the study programme were in the range of 1.1-1.6 l/m , with 

some variation between the respective test roads and the two phases of the 

study programme. 

The calcium chloride was applied as solid flakes in 1977 and as a liquid in 
1978, at a rate of 2-2.3 kg/m {3h-^ ton/mile) per strip. This application 
rate was equivalent to 0.64-0.67 kg CaCK/m of road surface. These 
application rates are normally used for dust control on rural roads. 

At the start of the 1977 phase of the study, the CaCl„ was applied to all 
test roads on June 17 and the application of the waste oil was made on June 
22, in both cases thp dates were selected depending on suitable 
weather conditions. During the 1978 phase of the work the field activities 
began earlier, with the CaCl^ being applied on May 18 and the waste oil on 
May 24. 

Traffic counters were installed on each test road to record the traffic 
density for the duration of each phase of the study programme. 

Weather data were obtained from the monthly summary reports issued by the 
Peterborough weather station, supplemented as required by field observations 

Of particular interest were the rainfall data and the effects of rainfall as 
a possible transport mechanism for the dust suppressants away from the road 
bed. 



During 1977 the routine sampling programme included once-monthly sampling 
at each of the four test roads, of the road bed, shoulders, roadside veg- 
etation and field soil. For the 1978 phase of the study, sampling was 
reduced to include only the road bed and shoulders on a bi-weekly basis at 
each of the two test roads. Samples of the road bed from road #3 were taken 
once monthly. 



2. PROCEDURES AND METHODS, (cont'd) : 

The "Coning and Quartering" method of sampling dry materials was used for 
sampling the road bed, and later also the shoulder and field soil, in place 
of a hand-held core sampler which proved ineffective under the local soil 
conditions. The section to be sampled was loosened to a depth of 10 cm 
over an area of 30 x 30 cm. This loosened material was then subjected to 
the coning and quartering procedure. Generally 3 - 5 of these grab samples 
per test section constituted a single composite sample for subsequent 
chemical analysis. Field soil samples were taken for each section of test 
road at distances of 10 m, 15 m and 25 m from the edge of the road. All 
field soil samples were Individual grab samples. 

Sampling of the roadside vegetation included broadleaf plants and grasses, 
located in approximately the same area as the shoulder soil samples. The 
species of broadleaf plants and grasses chosen for sampling were based on the 
abundance of the respective plants and their respective growing seasons in the 
various sampling locations. The grass sample was always a mixture of the 
common field grasses at each location. The broadleaf plants varied from 
section to section and between the several test roads. The vegetation sample 
always represented several plants or parts of several plants within the sel- 
ected sampling area. 

Dust sampling was an integral part of the study programme during both the 1977 
and 1978 phases. The main intention was to obtain an estimate of the quantity of 
settleable dust, within a reasonable distance from the edge of the road, e.g. 
5m. The sampling procedure may be considered as a modification of the 
standard ASTM procedure for the collection of particulate atmospheric fall-out 
ASTM designation D1739-70. The individual sampling devices were standard 
mason jars placed approximately 55cm above grade and at a distance of 5m from 
the edge of the road along both sides of each test section. The exposure time 
was 1 week at the end of which clean jars were placed in the respective holders. 
At road No. 4 these dust collectors were set up at distances of 5m, 10m and 25m 
from the edge of the road on both the east and the west sides of each test 
section. 

At the control section of Road 4 two standard type ASTM dust collectors were 
Installed in accordance with the procedure D1739-70. These units were placed 
5m from the edge of the road with the mouth of the cylinder 2.4m above grade. 
In accordance with the ASTM procedure the dust collectors were left in the field 
for consecutive periods of 1 month. 



2. PROCEDURES AND METHODS, ( cont 'd) : 

During 1978 two high volume air samplers were used to obtain samples of the 

suspended particulate in sufficient quantity to permit chemical analysis of 

the cdllected dust. Two high volume samplers were installed on Road 1, 5m 

from the edge of the road: One sampler on the north side of the oil section 

and the other on the south side of the CaCl section. 

2 

Both roads 1 and 2 were traversed by two small fast flowing streams, one each 
respectively in the oil section and in the CaCl^ section of each road. Each 
stream was inspected regularly for any evidence of run-off or leaching from the 
road bed, and water samples were taken upstream and downstream of the road in 
each location during or immediately after each heavy rainfall. 

Samples of run-off water from the road bed were collected at every opportunity 
during sufficiently heavy rains, near the point where the run-off water left 
the road edge and entered the ditch or the road shoulder. 

On a non-routine basis samples were taken of miscellaneous items such as oil coated 
stones which had been thrown on to the shoulder by passing cars, gravel that 
had been washed off the road, and run-off fines taken from the ditches and 
adjacent fields. These non-routine samples were to serve as evidence that 
measurable amounts of dust suppressant had left the road bed. 

Chemical analysis was made routinely for lead and oil (as HEM, hexane 
extractable material) to indicate the possible presence of waste oil, and for 
chlorides to show pbssible traces of CaCK. As necessary, control samples 
were analyzed for all three parameters. 

Samples of waste oil as applied were analyzed for HEM, specific gravity, and 
the following heavy metals, arsenic, cadmium, chromium, copper, lead and zinc. 
Gas liquid chromatography was used to determine RGB's. 

Samples of liquid CaCK were analyzed for pH, specific gravity, chloride 
content and the presence of oil measured as HEM. 



3. DISCUSSION OF OBSERVATIONS AND RESULTS : 

As this presentation intends to be an overview of the completed work, this 
section will of necessity have to be a short summary of the total data 

and any pertinent discussion, to Illustrate the more clearly evident trends 
in the data. 

The 1977 phase of the programme showed the elusiveness of the 3 main parameters 
of interest, by confirming initial trends as variations of background concen- 
trations rather than as significant trends. In part this was caused by the 
once monthly sampling programme and by sampling both field soil and roadside 
vegetation. It is for this reason that sampling of field soil and roadside 
vegetation was excluded from the 1978 programme. Besides, the summer of 
1977 had above average rainfall in the study area, therefore requiring little 
help from dust suppressants to maintain reasonable control of dusty roads 
and producing somewhat inconclusive dustfall data. 

Table 1 gives a summary of the traffic volume recorded during the 2 years of 
the study as overall average number of vehicles per day. Both roads No. 2 
and 3 were "^ery lightly travelled with increased traffic densities on roads 
No.l and 4. The increased traffic on road No.l during 78 compared to 77 was 
consistent over the period of observation. As a result of the low traffic 
volumes on all test roads, automotive exhausts could be disregarded as a 
measurable source of lead contamination in the roadside environment. Therefore, 
any concentrations of lead determined above the natural background values would 
be attributable to external sources of contamination, such as the materials 
used as dust suppressants. 

Rainfall during the period May to November 1978 was near average with respect 
to total rainfall, however June and July recorded below average rainfall, while 
August and September had above average rainfall with September showing a total 
precipitation of 133mm for 2 times the monthly average. 

The waste oil used for the 1978 study had a specific gravity of 0.923 and an 
oil content of approximately 70% by weight measured as HEM. The concentrations 
of lead and zinc were respectively 4.34 g/1 and 1.25 g/1 . Cadmium was present 
at 5.8 mg/1. Copper was present at 31.1 mg/1 , chromium at 12.5 mg/1 and 
arsenic at 29.5 mg/1 . 



3. DISCUSSION OF OBSERVATIONS AND RESULTS, (cont'd) : 

The GLC analysis showed that any PCB present in the waste oil would be below 
the detection limit of this method (5 mg/1). 

The calcium chloride used for dust control in 1978 had a specific gravity 
of 1.346 and a chloride content of 315 g/1 , corresponding to a CaCU content 
of 36.5% by weight. The liquid CaClp ^lad a trace of oil measuring 8 mg/1 
as HEM. 

The revised sampling programme used during 1978 for the road bed and shoulder 
soil provided 5 grab samples per test section for each composite sample at a 
frequency of once every 2 weeks. Inspite of a remaining fluctuation of data, 
a trend could be established providing a basis for data analysis and possible 
conclusions. 

The data in Table 2 indicate the variation of HEM content in road bed samples 
during the 1978 sampling period. The May samples were taken before application 
of the waste oil and showed the residual HEM in road 1 at 7.5 mg/g and 0.02 
mg/g in road 4, as the oil section of this road had been regraded in the early 
spring. The data show a general trend toward the pre-application level in 
the case of road 1. It is noted that road 4 did not decrease to the pre- 
application value, but stayed at a higher value than road 1. This pattern 
may be similar to that shown by road 3, where without further treatment in 
1978 the road bed showed a continuous decrease from 7 mg/g in June to 1.1 by 
March 1979. 

The lead present in the waste oil appeared to behave quite differently from 
the oil itself once exposed to conditions in the road bed, as shown by the 
data in Table 3. The data suggest a more or less random fluctuation 
rather than any identifiable trend and no gradual decrease of the lead con- 
centrations. Apparently lead was retained in the road bed aggregate. 

As shown In Table 4 the chlorides in the road bed increased as a result of 
the initial application on both test roads, followed by a gradual decline 
specially during the month of September with its above average rainfall. The 
disappearance of the chloride would be under influence of the rain water 
effecting the leaching of chlorides from the road bed aggregate. 



3. DISCUSSION OF OBSERVATIONS AND RESULTS, (cont'd) : 

The data thus indicated that both with oil treatment and with calcium 
chloride the materials added to the road bed for dust suppression were lost 
to the environment during the period of observation. Sampling of run-off 
water from the road bed as it entered the road shoulder or the roadside 
ditches gave confirmation of the transport route for these materials leaving 
the road bed as shown in Table 5. In the run-off water from the chloride 
treated sections chloride concentrations as high as 260 mg/1 were observed. 
From the oil treated sections HEM concentrations to 220 and 350 mg/1 were found. 
The \/ery low concentrations of lead agree with the concept that lead is 
retained in the road bed since the ratio HEM:lead in the run-off water was 
in the order of 4,000:1 compared to the waste oil sample showing a ratio of 
approximately 150:1. 

In addition to the run-off water samples a number of miscellaneous samples 
have been collected and analyzed, to obtain analytical evidence of the 
presence of either oil or calcium chloride in areas away from the road bed. 
Table 6 presents a brief summary of this information. The stream sample 
was taken downstream of road 1 in a stagnant area just upstream from where 
a tributary joined the stream. The 90 mg/1 HEM content provides confirmation 
of the observed oily scum accumulated in that location. The other samples 
presented in Table 6 represent areas of visible contamination with waste oil 
and the results at least confirm the presence of oily material. It is 
interesting though that the actual numbers were equal to or lower than the 
road bed oil concentrations, except for one sample. 

A totally separate study could be made of the subject of dust generation, 
sample collection and chemical analysis in relation to processes occurring 
in the road bed under influence of traffic usage. Particulates in automotive 
exhausts would need to be considered as well, 

The data in Table 7 show that the high volume air samplers collected dusts 
with somewhat similar chemical characteristics, although the sections of road 
were typically different, oil treated vs CaCl^ treated. It is noted that 
both the HEM and the lead contents of both types of dust are very much 
higher than recorded for the road bed samples. 



3. DISCUSSION OF OBSERVATIONS AND RESULTS, (cont'd) : 

For comparison Table 7 also presents chemical characteristics of dust 
samples obtained from the dustfall collectors, specifically with respect to 
the lead content. Although the measured lead concentrations in the dust 
samples are significantly lower than those obtained for the high volume air 
samplers, the dust lead content is still higher than the corresponding values 
found in the road bed samples. 

Some clarification of the problem may be obtained from a study of the results 
in Table 8, which show the penetration of materials into the road bed. The 
highest concentrations of all three parameters were found in the upper 2.5 cm 
layer. This feature applied particularly to the lead but also to the HEM. 
It would seem that the lead remains in the upper layer of road bed surface 
material, and that this layer produces most of the dust. It was reassuring 
to find that the average concentrations of constituent for the upper 10 cm layer 
based on the data in Table 8 compared well with the road bed samples taken 
during the same period represented by each of the depth profiles. 

4. SUMMARY : 

From the data collected during the study programme, some of which we have 
reviewed in this presentation, we have prepared the following summary. 

4.1 Any PCB's present in the waste oil used in 1978 were below the 
5 ppm detection limit of the GLC. 

4.2 The observed loss of waste oil from the 1978 test roads was approx- 
imately equal to the quantity of waste oil applied in 1978. 

4.3 The prime transfer route was via the run-off water during rainfall, 
which resulted in some accumulation in the adjacent road shoulders. 

4.4 After a single application of waste oil for dust control, oil losses 
from the road bed continued into the second year, with a residual oil 
content still above the background level. The dust control effective- 
ness was lost within 6 months after the application. 



11 



4. SUMMARY, (cont'd) : 

4.5 Samples of run-off water showed oil concentrations consistently 
above the MOE objectives of 15 mg/1 HEM for industrial waste dis- 
charges to receiving streams. 

4.6 Oil-coated fines were found in adjacent shoulders and fields, as 
temporary storage areas for continued transport from there with the 
run-off water. 

4.7 Lead compounds present in the waste oil seemed to be retained in the 
road bed aggregate and showed a very slow rate of loss compared to 
the oily materials. 

4.8 Dust analysis showed higher concentrations of HEM and lead per gram of 
dust than in the road bed. Dust collected with the high volume air 
samplers showed similar high concentrations of materials for both the 
oil and CaCl^ sections. 

4.9 The lead content of settleable dust was consistently higher for the 
oil treated section than for the control or CaCl sections, likely 
as a result of the oil treatment. 

4.10 Loss of chlorides from the CaClp treated roads was effected mainly by 
rainfall and run-off and subsequent discharge to the receiving stream. 
Most of the applied chloride was lost from the test roads during the 
first 5 months after application. 

4.11 Analysis of settleable dust data indicated that dust control with 
waste oil was equally effective as that using CaCl„. Treatment with 
CaCl^ allowed the road surface to retain its dust control charac- 
teristics even after regradlng. 

4.12 We have found that materials for dust control are lost from the road 
bed under Influence of rainfall and run-off, independent of whether 
the material is soluble in water. Entry into the local road envir- 
onment will follow the local drainage pattern, perhaps with intermediate 
storage areas. Eventual discharge Into nearby receiving streams or 
lakes can be expected. 



12 



4. SUMMARY, (cont'd) : 

4.13 The scope of this study programme did not permit an assessment of 
the environmental effects, due to the short period of observation 
and the low levels of material transferred into the roadside 
environment. Complex physical chemical reactions must be taken 
into consideration, covering the exposure of soil, sand, gravel 
and vegetable matter to inputs of organic and/or inorganic chemicals, 
when attempts are made to predict the transport of materials from the 
road bed into the roadside environment and their possible effects on 
that environment. 




o 



ROAD 1 



Ar 



AT 






FIGURE NO. I 



1^ 



TABLE 1 




TRAFFIC VOLUME 


VEHICLES PER 


DAY 



ROAD 


1 


2 


3 


4 


1977 
1978 


1 

79 

112 


15 


13 


70 
72 



TABLE 2 



OIL IN ROAD BED 
mq HEM/g 



DATE 


Road 1 


Road 4 


Road 3 


1978 








May 


7.5 


0.02 


- 


June 


19.5 


14.0 


7.0 


July 


14.4 


10.5 


6.7 


Sept. 


10.4 


7.5 


3.2 


Oct. 


9.4 


6.5 


3.4 


March, 1979 


7.4 


8.3 


1.1 


Control 


0.1 


0.44 


0.05 



TABLE 3 
LEAD IN ROAD BED 

mil 



15 



DATE 


Road 1 


Road 4 


1978 






May 


0.10 


0.03 


June 


0.14 


0.13 


July 


0.12 


0.10 


September 


0.09 


0.10 


October 


0.11 


0.09 


March, 1979 


0.15 


0.11 


Control 


0.03 


0.05 



TABLE 4 
CHLORIDE IN ROAD BED 
mg/g 



DATE 


Road 1 


Road 4 


1978 






May 


0.02 


0.01 


June 


2.6 


0.8 


July 


2.9 


2.3 


August 


2.1 


1.4 


September 


0.2 


0.5 


November 


0.1 


0.03 


Control 


0.09 


0.04 



TABLE 5 
RUN-OFF WATER 

mq/l 



16 





CaCl^ 


OIL 




Road 1 


'77 


150 CI 




. 


Road 1 


'78 


24 CI 


220 HEM 


0.06 Pb 


Road 4 


'78 


- 


150 HEM 


0.02 Pb 


Road 2 


'77 


260 CI 


350 HEM 


- 



TABLE 6 
MISCELLANEOUS SAMPLES 
OIL SECTION 



1978 


HEM 




Road 1 Stream 


90 mg/1 


0.1 mg/1 Pb. 


Road 4 Shoulder fines 


6.3 mg/g 




Road 4 Run-off fines 


0.72 mg/g 




Road 4 Shoulder soil 


2.15 mg/g 




Road 4 Shoulder soil 


45.0 mg/g 


1 



TABLE 7 
DUST CHARACTERISTICS 



17 



1. 


High Volume air Sampl 


ers 








1.1 


Oil Section 


Average 




Maximum 


Minimum 




dust mg/h 


9.8 




33.6 


2.2 




HEM mg/g 


96 




479 


8.8 




Pb mg/g 


2.8 




4.53 


0.49 


1.2 


CaClp Section 












dust mg/h 


13.7 




50.6 


2.6 




HEM mg/g 


55 




193 


4.2 




Pb mg/g 


2.0 




3.55 


0.19 




CI mg/g 


6.3 




10.6 


0.85 


2. 


Dust Collectors 










2.1 


Oil Section 












2 
dust g/m /day 


0.14 




0.18 


0.10 




Pb mg/g 


0.53 




0.71 


0.35 


2.2 


CaCl„ Section 

2 
dust g/m /day 


0.25 




0.29 


0.20 




Pb mg/g 


0.07 




0.09 


0.04 


2.3 


Control 












2 
dust g/m /day 


0.38 




0.45 


0.22 




Pb mg/g 


0.15 




0.17 


0.12 


3 


Road Bed oil 


0.09 


mg/g 


Pb 






CaCl^ 


0.03 


mg/g 


Pb 






Control 


0.03 


mg/g 


Pb 


1 



TABLE 8 
PENETRATION INTO ROAD BED, mg/q 



18 



Depth 
cm 


June 
HEM 


Oil Section ^ ^ .. 

October 

Pb HEM Pb 


CdCl^ 

June 
CI 


Section 

October 
CI 


- 2.5 


29.9 


0.25 


14.3 0.17 


4.9 


0.7 


2.5 - 5 


9.0 


0.06 


9-4 0.09 


3.2 


0.5 


5 - 10 


8.8 


0.07 


1.6 0.05 


0.45 


0.5 


10 - 15 


6.8 


0.06 


1.6 0.13 


0.22 


0.6 


15 - 20 


4.1 


0.08 


1.3 0.07 


o.u 


0.3 


20 - 25 


1.3 


0.03 


0.57 0.04 


0.04 


0.3 


25-30 


0.12 


0.02 


0.12 0.02 


0.02 


0.1 



19 



THE EFFECTS OF ROAD OILING ON 
PCB ACCUMULATION IN AQUATIC LIFE 

LTS 80-5 



K. Suns, C. Curry, D. Wilklns and G. Crawford 
Ontario Ministry of the Environment 
Box 213, Rexdale, Ontario 
September, 1980 



20 



TABLE OF CONTENTS 

page 



n 



PREFACE 

SUMMARY 

INTRODUCTION 1 

METHODS 

Fish Residue Investigations 1 

Caged Freshwater Clams - Dickie Lake 4 

Sediments g 

RESULTS AND DISCUSSIONS 

Fish Residues 8 

Caged Freshwater Clams 8 

Sediments 10 

CONCLUSIONS AND RECOMMENDATIONS n 

LITERATURE CITED 12 

ACKNOWLEDGEMENTS 13 



21 



PREFACE 

During the past few years there has been growing concern over 
the increasing numbers of fish contaminants in Ontario lakes and rivers. 
Many contaminants reach concentrations in fish which pose a risk for 
human consumption, while the health of the fish themselves does not 
appear to be affected. Consequently, human consumption of fish from 
some waters must be controlled because of their content of materials 
such as mercury or PCB's. 

Effective major fish analyses programs have been directed toward 
the sport fish populations in order to develop appropriate human consump- 
tion guidelines. However, due to ageing difficulties and their wide- 
ranging life-style contaminant residue data of adult fish do not shed 
much light on some fundamental questions regarding contaminant control, 
such as location of sources, trends with time and mechanisms of uptake. 

To augment the adult sport fish surveys, the Toxicity Unit began 
in 1975 to conduct contaminant surveys of young fish. The program 
concentrates on young-of-the-year, or yearlings of a variety of species. 
Such fish can be easily aged and they represent current contaminant 
uptake conditions. The young fish have a limited range, so their 
contaminant uptake represents also a narrow range of space conditions 
While the results may not be relevant to human consumption of sport fish 
from the same waters, they provide good scientific data for determining 
contaminant uptake as a function of time and geographic location. 

This concept is being applied to investigate a number of areas 
of concern in the Province. The young fish surveys are supported by a 
variety of chemical and biological collections to suit the specific 
purpose of the investigation. 

This report deals with the practice of waste oil use for dust 
control and its effect on PCB uptake in yellow perch and freshwater clams 
in the receiving waters. 



22 



Summary 

PCB residue concentrations were determined in yearling yellow 
perch frorr twelve Muskoka lakes to evaluate the effects of road oiling 
on PCB uptake. Fish residue analyses have shown that PCB's were signi- 
ficantly (P <0.05) elevated in lakes that were affected by the run-off 
from waste oil applications. Furthermore, 71% of all the fish: sarrples 
analyzed from lakes affected by road oiling exceeded the PCB guideline 
for wildlife protection (I.J.C. 1977). while PCB residues in non-affected 
lakes were considerably lower, 

A study using freshwater clams in Dickie Lake demonstrated that 
PCB uptake in the nearshore biota was affected by drainage characteristics 
and the proximity of waste oil application sites to the receiving waters. 
Although the PCB residue concentrations in waste oils applied were 
considerably below the Ontario Pollution Prevention Guideline of 25 ppn, 
a significant (p <0,05) uptake of PCB's was observed in caged freshwater 
clams. 

Stream sediment analyses shewed that the highest PCB concentrations 
existed immediately below the oiled road in the stream bed. 



23 



INTRODUCTION 

Although the practice of using contaminated waste oils for dust 
control is well established, little is known of the environniental impact 
associated with it. A report prepared for the Ontario Ministry of the 
Environment and Ministry of Transportation and Communications on the Effects 
of Waste Oil as a Road Dust Suppressant (L.S. Love & Associates 1978} 
concludes that runoff is the major route for transfer of waste oils from 
the road surfaces. Therefore, it can be expected that any contaminants 
in waste oils will eventually be discharged to surface waters. EPA's 
Water Quality Research Laboratory in Edison, N.J. (Waste Oil Fact Sheet) 
has also demonstrated that about 99^' of the oils applied to rural road 
surfaces left the surfaces either as dust particles or in v/ater runoff. 
While the waste oil movements were docurrented by both studies, the effects 
on the aquatic life in receiving waters have not been evaluated. 

the presence of PCB residues in waste oils and the repetitive 
nature of road oiling in Ontario has raised questions regarding the 
possibility of PCB accumulations in the aquatic biota. The concerns over 
present road oiling practices have been documented by L.S. Love and 
Associates (1978), and the study concludes that the potential for 
receiving water contamination exists. 

The present study was initiated following observations of anomalous 
PCB residue distributions in yearling yellow perch from Muskoka lakes. 

METHODS 

Fish Residue Investigations 

In order to explain elevated PCB residues in fish from some 
Muskoka lakes used only for recreational purposes, PCB residue concentra- 
tions in fish from areas with known road oiling activities were compared 
with fish residues from lakes where oiling was not practiced. Twelve 
Precambrian lakes were used for the survey and were classified either as 
affected or not affected by waste oil applications (Fig. 1). Table 1. The 

criterion used for lake separation was the presence or absence of road oiling in 

lake drainage basins, as shown by tovjnship road oiling 

records. No attempt was made to quantify waste oil applications 



TABLE 1, 



COMPARISONS OF PCB RESIDUES IN YEARLING YELLOW PERCH FROM 
OILED AND NOT-OILED WATERSHEDS 



Locality 


N* 


Fish Size T.L. 
(mm) 


Fish \ 


•ie 
3) 


ight 


10 


Fat 


PCB Cone 
(ng/g 


Bntration 
± S.D.) 


Not Oiled 














Cranberry Lake 


7 


106 


+ 


1 


12.9 


+ 


3.5 


5.2 


+ 


1.4 


38 ± 


16 


Bigwind Lake 


6 


74 


+ 


6 


3.6 


+ 


1.0 


2.R 


± 


0.4 


10 ± 


19 


Cnub Lake 


9 


82 


+ 


6 


5.2 


+ 


1.3 


2.4 


+ 


0.4 


Trace 


Leonard Lake 


TO 


7b 


± 


3 


3.9 


+ 


0.6 


2.4 


± 


0.9 


Trace 


lielson Lake 


10 


82 


+ 


3 


4.b 


+ 


1.4 


2.1 


+ 


0.3 


n ± 


12 


Ciled 


























Duck Lake 


9 


97 


+ 


3 


a. 2 


+ 


1.0 


2.4 


+ 


0.5 


79 ± 


14 


Healey Lake 


10 


S3 


4- 


2 


5.5 


-1- 


0.5 


5.0 


+ 


0.2 


89 ± 


45 


Harp Lake 


■ 10 


65 


± 


3 


2.4 


± 


0.3 


1.2 


+ 


0.1 


101 ± 


53 


Fawn Lake 


10 


88 


+ 


4 


6.3 


± 


1.0 


3.9 


+ 


0.4 


146 ± 


56 


Little Clear Lake 


10 


70 


+ 


3 


3.2 


+ 


0.5 


3.3 


+ 


0.4 


172 ± 


67 


Heeney Lake 


10 


79 


-+- 


2 


4.2 


+ 


0.3 


3.0 


+ 


0.4 


256 ± 


84 


Dickie Lake 


10 


67 


+ 


3 


2.6 


+ 


0.4 


3.3 


+ 


0.3 


307 ± 


70 



*Each sample is a composite of 8 fish. 
Detection Limit 



10 ng/g 






8I°00V 



Nelson 



SUDBURY 



SCALE 




500 1500 3000 4500 M«tr«s 



45»I5'(V 



Cranberry 

L. 



CARNARVON 



h 



Duck 
L. 



FIGURE I STUDY AREA.MUSKOKA LAKES 



26 



in individual drainage basins. 

Samples of young yellow perch ( Perca flavescens ] were collected 
for body-burden deteminations. Individual fish were measured, weighed 
and scale samples taken from representative size groups. Fish ageing 
confirmed that all samples belonged to the yearling (1+) age class. The 
selection of a specific age class provided residue data that were 
spatially comparable. Composite samples of 8 fish each per site were 
wrapped in hexane-washed aluminum foil and frozen In the field. PCB 
residues were determined for conposite whole fish samples, and analytical 
results were reported on a wet-weight basis. Student's "t" tests were 
done to compare differences between means. All analyses were done at 
the Ministry of the Environment Pesticides Laboratory at Rexdale by gas- 
chromatography methods. Detailed methodologies are available from the 
Handbook of Analytical Methods for Environmental Samples, Laboratory 
Services Branch, Ontario Ministry of the Environnent. 

DICKIE LAKE STUDY 

Caged Freshwater Clams 

In addition to the fish residue Investigations, a study was 
undertaken at Dickie Lake In 1979 to assess site-specific effects of 
road oiling. Caged freshwater clams ( Elliptio complanata ) were used 
to evaluate PCB uptake at three nearshore sites in the lake (Fig. 2). 

Live freshwater clams were collected from Balsam Lake In Bexley & 
Fenelon Township and transferred to Dickie Lake. PCB concentrations 
in Balsam Lake clams were typically at trace levels, and therefore may 
be considered representative of background conditions. Each clam was 
individually measured and weighed, and 15 clams were placed in each 
wire cage (22 x 21 x 15 cm). Caged clams were placed on lake sediments 
near Dickie Lake inflows #8, ^9 and the lake outflow at locations CI, 
C2 and C3 (Fig. 2). Clams were located at site CI adjacent to the 
oiled road on two occasions, first (June 5-19) prior to the season's 
oil application and secondly (June 19-July IC) after oiling. Road oiling 
was carried out on the 18th of June. The Initial exposure was 
intended to evaluate PCB uptake from previous season's residuals. 



27 



INFLOW 10 



INFLOW 9 




LEGEND 



S5 - SAMPLING STATIONS 

TYPE 

S- SEDIMENTS 

C-CLAMS 



FIGURE 2 ■■ DICKIE LAKE SITES 



28 



PCB's and fat content determinations were done by azeotropic distniation 
using benzene. Details of the analytical methodologies employed are 
available from the Handbook of Analytical Methods for Environmental Samples. 
Laboratory Services Branch, Ontario Ministry of the Environment. 

Sediments 

Sediment samples were collected at ten sites for PCB 
analyses (Fig. 2). Most samples were obtained with a 5 cm diameter 
push-rod corer of Water Resources Branch design, but Station S9 was 
sampled with a 23 x 23 cm ponar dredge. The control site (SI) was 
located about 50 meters upstream of the perimeter road on inflow #8 in 
a marshy area with very organic soils. Downstream from the road and 
around the perimeter of the lake the sediments were predominantly sandy 
with varying fractions of organic detritus. Some construction activity 
just downstream from the road (installation of a weir on i^8 Inflow) may 
have induced recent siltation 1n the stream, but visual cbservatiors 
revealed only minor silt deposits. 

Station S9 in a deep sheltered basin was the only lake station 
sampled which represented a true depositional environment. Any contaminants 
in the nearshore sands would be indicative of fairly recent inputs that 
would ultimately be resuspended and transported to a depositional area. 

Core samples were of varying lengths due to variations in sediment 
types and the inability of the push-rod corer to penetrate through roots, 
stones and clam shells. Cores were extruded directly into wide mouth 
glass jars, one sample for the top half of the core and one sample fcr 
the bottom half. Details of core lengths are given in Table 3. 

In addition to PCB's, the sediments were analyzed for n-ercury, 
copper, zinc, lead, aluminum and nickel. All analyses were done at the 
Ontario Ministry of the Environment Laboratories in Rexdale. 



TABLE 3. 



PCB RESIDUES IN DICKIE LAKE 
SEDIMENTS - 1979 



Station No. 



Depth Interval 



Description 



PCBs (ug/kg) 



Station 1 
Upstrean Control 

Station 2 Roadside 

Station 3 

Stream half way to lake 



Station 4 
Stream Mouth 

Station 5 



Station 6 



Station 7 



Station 8 



Station 9 

Station 10 
Lake Outlet 

Detection Limit 



Surface to 10 cm 
10 cm to 20 cm 

Surface to 5 cm 



Surface to 10 cm 

1 cm to 1 5 cm 

Scoop of Surface 2 cm 

Surface to 9 cm 
C cm to 20 cm 

Surface to 12 cm 

12 cm to 24 cm 

Surface to 10 cm 
25 cm to 35 cm 

Surface to 6 cm 

6 to 16 cm 

Surface to 13 en 

13 to 26 cm 

Ponar Surface to 5 cm 

Surface to 8 en 
8 to 15 cm 



Highly Organic 
Black Silt 



NO 
KD 



Brown Organics Sand with PvOots 1000 



Coarse Sand over Organic Silt ND 

200 

Loose Organic Silt 240 

Coarse Sand & Org. ND 

Med. Sand h Org. 20 

Medium Sand & Org. 20 

over Fine Sand NO 

Fine Sand Some Organic Debris KU 

Fine to Coarse Sand KD 

Vegetation over Sand with 

Pyrites ND 

Sand m 

Sand with Trace Org. ND 

Fine Sand ND 

Organic Silt Coze 150 

Vegetation over sand ND 

Coarse Sand and Organic Debris ND 

10 



N.D, - Non detectable 






30 



RESULTS AND DISCUSSIONS 
Fish Residues 

Mean PCB residue concentrations In yearling yellow perch from 
lakes where road oiling occurred, rarged froni 79 - 307 ng/g; whereas 
fish residues from lakes where oils were not used on roads as dust 
suppressant ranged from 3-38 ng/g (Table 1). The respective neans for 
each group were 166 ± ICC ng/g and 12 ± 15 ng/g (p <0.05). The typical 
composition of PCB residues in fish were Aroclcrs 1254 and 1260 in a 4:1 
ratio. 

Since iretabolic rates, exposure times and contaminant concentrations 
govern contaminant uptake in fishes (de Freitas 1976; Nebeker 1975; Kelso 
and Frank 1974), a degree of uniformity of fish sizes, ages and lipid 
contents is necessary for valid spatial contaminant level comparisons. 
The use of yearling yellow perch as a biological integrator satisfies 
these criteria. The collection of a specific age class has ensured a 
similar exposure period, and the absence of statistically significant 
(p >0.05) correlations between PCB residues in fish, their sizes and 
lipid contents suggest that PCB residue differences cannot be attributed 
to differences in metabolic activity. It may be concluded, therefore, 
that the major differences in PCB residue concentrations in fish were 
related to PCB availability. 

The I.J.C. (1977) guideline (IOC ng/g) for PCB's in fish, 
established for the protection of wildlife and fish-eating birds were 
exceeded in 71% of the lakes affected by road oiling, whereas fish 
residues in the non-affected lakes remained well below this guideline 
limit. PCB concentrations in yearling yellow perch from these recreational 
lakes were of the same order of magnitude as residues found in lakes with 
known industrial or municipal PCB inputs, such as Lake Simcce and Lake 
Muskoka (Suns et_ al_. 1978), or several industrialized sites on Lake Ontario 
(Trenton - 346 ng/g; Moira River - 308 ng/g; Cornwall - 138 ng/g). 

While the fish residue data from this survey demonstrate that 
PCB inputs from waste oil applications have significantly influenced 
PCB residue concentrations in nearshore fishes of tlie receiving waters, 
the degree and extent of PCB accumulation in adult sportfish remains 
undetermined. 



TABLE 2. 




PCB 


UPTAKE 


RESULTS : 


IN 


GAGED 


FRESHWATER CLAKS 
















DICKIE 


LAKE - 


1979 










Stn. 
No. 


5 


« 


Clam Size 
(mm) 

73 ± 1 




^ 


Clarr Weight 

(g) 


% Fat 


PCB 


Concentration 

(ng/g) 


Pre-Oiling 


CI 


6.8 ± 0.7 


1.0 ± 0.2 




N.D. 


Post-Oil ir.g 


CI 


§. 




70 ± 1 






6.6 ± 1,0 


0.8 ± 0.2 




19 ± 4 




C2 


5 




74 ± 1 






7.9 ± 0.8 


0.9 ± 0.2 




15 ± n 




C3 


5 




74 ± 4 






7.3 ± 1.2 


1.0 ± 0.3 




Trace 



N.D. - Non detectable 
Detection Limit 



10 ng/g 



^ 



32 



Caged Freshwater CTams 

No PCB residue accumulations were detected in freshwater clans 
after a 14 day exposure at Dickie Lake inflow #8 (CI) prior to the 1979 
road oiling activities (Table 2). Lack of PCB residue accumulations 
from previous season's oiling activities indicates that PCB inputs cati 
be effectively reduced if alternative dust-control practices were 
implemented. Freshwater clam evaluation studies have shown that a 
14 day exposure period is long enough to demonstrate a measurable PCB 
uptake (Curry 1977). Following the road oiling on June 18, and after 
a 21 day exposure, significantly higher (p <0.5) PCB accumulations 
were detected in caged clams at site CI (19 ng/g) and site C2 (15 ng/g), 
compared to site C3 (2 ng/g) at the lake outflow. Both sites CI and C2 
were exposed to runoff from v;aste oil applications, whereas site C3 was 
not. These results suggest that PCB residue runoff fron- oiled road 
surfaces affects PCB accumulations in the nearshore biota. The effects 
are site-specific, end it appears that PCB residuals from prior season's 
applications did not affect residue accumulations significantly. It is 
interesting to note that soil sample analyses from Dickie Lake road 
showed PCB concentrations ranging from 12.6 ppm - 20.0 ppm in the oils 
used in 1979. These levels were below the Pollution Prevention 
Guidelines (1976) level of 25.0 ppm, yet a significant uptake of PCB's 
by the freshwater clams was observed in nearshore waters. 

Sediments 

No PCB's were detected in the sediments at the upstream control 
site (SI), while elevated PCB concentrations were found downstream of 
the road, with the highest concentrations closest to the oiled road 
(Stn. S2), as shown in Table 3. The PCB residues found resembled a 
one-to-one trixture of Aroclor 1254 and 1260. PCB residues were still 
twice the detection limit at the stream mouth (S4) and about 60 metres 
down the shoreline (S5), in spite of the predominantly sandy nature of 
the sediments. He PCB's were detected at the other sandy nearshore 
stations including the bay near the lake outflow (SIO). PCB residues 
from the deep basin sediments of the lake (S9) at 150 ug/kg showed 
convincingly that PCB's accumulate in the lake in association with the 



33 



fine grain-sized material. In comparison the mean PCB concentration 
for Lake Ontario sediments, a lake with known PCB inputs, has been 
reported to be 57 pg/kg (Frank et_ aj^. 1979), while PCB residues for 
Lake Huron sediments ranged from 9-33 yg/kg (PLUARG 1978). 

In order to determine the potential metals inputs from waste 
oil applications, metals residues from Dickie Lake sediments were 
compared to metals data from lakes not exposed to waste oil inputs. 
It was found that lead (=:3-130ug/g) , copper (<3-24 yg/g), zinc (5-170 yg/g), 
nickel (<3-10 yg/g)» mercury (<.01-.52 yg/g) and aluminum (1-10 mg/g) con- 
centrations in Dickie Lake sediments were not outside the typical metals 
ranges found in other Muskoka lakes (P. Dillon, personal comm.). There- 
fore it may be concluded that waste oils were not a major contributor of 
metals in the Dickie Lake watershed. 



34 



CONCLUSIONS AND RECOMMENDATIONS 

PCB residues in juvenile yellow perch were found to be significantly 
elevated in watersheds where waste oils were used for dust control, as 
compared to lakes where road oiling was not practised. Fish residue 
concentrations in 71°^ of all fish samples analyzed from lakes affected by 
road oiling exceeded the PCB guideline established for the protection of 
wildlife and fish-eating birds. 

PCB uptake results from the caged clam study in Dickie Lake showed 
that PCB accumulations in nearshore biota were affected by drainage 
characteristics and the proximity of oiled roads to receiving waters. 
The caged clam study results also suggest that PCB residuals from prior 
season's waste oil applications do not affect residue accumulations 
significantly. 

It should be noted that significant PCB accumulations in the 
near-shore biota resulted from waste oil applications that contained PCB 
residues below the existing Pollution Prevention Guideline of 25 ppm. 
Therefore the PCB content in waste oils should be reduced in cases where 
the receiving waters d.re affected by run-off from waste oil applications. 

While this study has demonstrated that waste oil applications do 
enhance PCB uptake 1n the biota of receiving waters, the impact on the 
sport fishery remains unknown. A PCB residue survey of adult sportfish 
in selected Muskoka lakes is planned for the 1980 field season. 



35 



REFERENCES 

CURRY. C. 1977-78. The freshwater clam ( Elliptlo complan ata). a practical 
tool for monitoring water quality. Water Pollution Research 1n 
Canada. Vol. 13:45-51. 

(leFREITAS. A.S.W. A model for pollutant accumulation by fish. Ottawa 
River Project. Report No. 3, January 1976. University of 
Ottawa - National Research Council of Canada. 

FPMK, R., R.L. THOMAS. M. HOLDRINET. A.L. KEMP and H.E. BRA.UN. 1979. 
Organochlorine insecticides and PCB in surficial sediments and 
sediment cores. Journal for Great Lakes Research. Vol, 5, No. 1. 

I.J.C. 1977. New and Revised Great Lakes Water Quality Objectives. 
Vol. 2. October 1977. 

LOVE. L.S. I ASSOCIATES CANADA LIMITED. "Report on the Environmental 
Effects of Waste Oil as a Road Dust Suppressant" - for the 
Ontario Ministry of the Environment, Pollution Control Branch, 
Toronto Report #595, March 1978. 

NEBEKER, A.V. 1976. Summary of recent information regarding effects of 
PCB's on freshwater organisms. Proceedings of National Conference 
on Polychlorinated Biphenyls. 1976. E.P.A, Office of Toxic 
Substances. 

PLUARG, 1978. Environmental Management strategy for the Great Lakes System. 
International Joint Commission 1978. pp. 39-40. 

POLLUTION PREVENTION AND WASTE MANAGEMENT GUIDELINES FOR POLYCHLORINATED 
BIPHENYLS. Ontario Ministry of the Environment, Waste Management 
Branch. September, 1978. 

SUNS, K.. M. JACKSON, G.A. REES and R. McVICARS. 1978. The use of yearling 
yellow perch as indicators or organic chem.icals and mercury 
contann'nation in selected Ontario lakes. Ontario Ministry of 
the Environment. LTS 79-3. 1978. 

"WASTE OIL FACT SHEET" prepared by Industrial Analysis Office. Energy 
Conservation and Environment, Federal Energy Administration, 
Washington, D.C. 20461, June 1976. (ref. for the EPA's Water 
Quality Research Laboratory in Edison, N.J.). 



36 



AcknowTedgenents 

We thank D. Andrews and F. Hedley for their assistance with 
sample collections. 

We are especially indebted to A.F. Johnson for valuable ideas 
and the necessary background for road oiling activities. 

Dr. T. G. Brydges and 6.R. Craig supplied valuable comments 
and criticisms on the manuscript. 



37 



Implications and Actions in i E. W. Turner j 
Regard to Road Oiling i Waste Ma nagem ent Br.| 

\miL OIL UTJUZAnOM 

1975 - MINISTRY OF ENERGY FORfiED 

- PROJECT DEVELOPED TO STUDY WASTE 
OIL UTILIZATION 

- FOLLOWED FROM FEDERAL/PROVINCIAL STUDY 
ON BURNING OF WASTE CRAi'IKCASE OIL 

IN CEMENT KILiJS 

LASK FORCE OR COmiTTEE FORNED 

riIN. OF ENERGY 

filN. OF TRANS, 5 COMM, 

niN, OF IND. & TOURISM 

MIN. OF ENVIRONMENT 



OBJECTIVE 



TO REVIEW WASTE OIL SITUATION AND 
MAKE RECOMMENDATIONS ON POLICIES FOR 
WASTE OIL UTILIZATION. 



38 



yASI£ OIL RE£YaiiiG SMY 

1975 l EKNEKRQ Ji IK. RETAINED TO STUDY WASTE 
OIL RECYCLING POTENTIAL 



OBJECTIVES 



- COMPILE DATA OH AMOUNTS OF 
WASTE OIL GENERATED 

- REVIEl* REREFINING PROCESSES 

- COST 

- PRODUCT ACCEPTABILITY, 

- ENVIRONMENTAL IliPACTS OF REREFINING 
PROCESSES 

- REVIEW ALTERNATIVE TECHNOLOGIES 

FOR UTILIZATION OR DISPOSAL OF WASTE OIL 



REPORT COMPLETED IN flARCH 1976 



39 



fimi.LMhS or l.FKNPPRflM .RFJML 

1) WASTE OIL VOLUfiFs (IJlPiUr.A i i [.jf, ,)ii.) 
10 MILLION GALLONS- !N ONTAKiO 

WI '-IILLION GALLOilS,. ?[.\{ YLAK SOLH 

5S mLLin^l GALLONS I'LR YLAH CONSUMFn (ESTIMATE) 

22 MILLION GALLONS LLk YLAR NNACGOdNTEl) 

2 ) C URRENT DISPOSAl OF WA^FJjTJ, 

- ROAD OILING - 6-7 MIL 

- BURNING AS FUEL - 2-3 MIL 

- REREFINING (RRESLUHE) - LO-LS MIL 

3 ) RE REFINING PROCESS 

1) DEMYDRAT ION/CLAY (RPCOMMENnED) 

2; 111 SliLLAFl ON/CLAY 

3) UiSIILLATlON/HYIlROIREATMLNT 

%i Ai:n)/CLAY 

V) EXTRACT ION/AC in/CLAY 

RANKED AS ABOVE ON FOLLOWING CRITERIA: 

- ENVIRONMENTAL - 20Z 

- QUALITY OF PRODUCT - 20% 
■ ^ PRODUCT RANGE - 5^ 

- FEED STOCK AVAILABILITY AND MARKET ASSESSMENT - 157. 

- ECONOMICS - /i[r/ 

EACH PROCESS FOUND TO HE PRACFICARLE ALTHOUGH ACID/CLAY 
FOUND TO RE MARGINARLF- 



40 



FINDINGS OF TEKNE RR ON RFPO RT (CnNTMLl 

4 ) ALTERNATIVE DISPOSAL O R USE TECHNOLO GIES 

A) BIODEGRADATION RY SOIL MICROORGANISMS 

B) THERMAL nESTRllCTION (INCINFRATION AS WASTE) 

C) BLENDING WITH FUEL OIL OR COAL 

D) USE AS FUEL -- CEfiENT KILNS, MlIN . INCIN. 

E) USE IN ASPHALT 

F) USE AS DUST SUPRESSANT -- ROAD OILING- 

5) ROAD OILING - FINDINGS AND CONCERNS 

A) 70-75% WASHED AWAY RY RAIN 

25-30% VOLATILIZATION, VEHICLE ADHESION 
11 LEFT ON ROAD 

B) OIL MAINLY CONFINED TO TOP ONE INCH 

C) HIGH CONCENTRATION OF LEAD IN ROAD SURFACE 

D) HIGH LEVELS OF LEAD IN ADJACENT PLANT LIFE. 

THESE FINDINGS BASED ON U-S- STUDY BUT SEVFRFLY CRITICIZED 
FOR LIMITED DATA. GENERALIZA [jonS, FTC. 

RECOMMENDED THAI FURTUFR ^T^1,3IES \\f llNDFiU'AKFN fO DFTFImInE 
ECOLOGICAL CONSLQUhNCFS n^ OIL RUNflFF- 

OTHER CONCER NS 

- PNA'S (POLY NUCLEAR AR'if^ATICS) KNOWN CARCINOGENS 

- OTHER UFAVY MFiALS - VANADIUM 

- nANfiANFSF 



41 

ACTION BY TASKFilRCF 

- PCB'S ALSO IDL:'^TIF]ED BY ^L AS SIGfJIFICANT 
COMPONEi^T OF WASTE OIL IN ONTARIO 

- TEKNEKRON CONCERNS OVER; LEAD 

PNA 

HEAVY riETAL 

- TEKNEKRON RECOMMENDATION FOR ECOLOGICAL 
STUDIES ON OIL RUN-OFF 



RECOMMENDATION DEVELOPED BY TASK FORCE INCLUDED 
A PROPOSED BAN ON ROAD OILING. 

TASK FORCE RECOMMENDATIONS NOT ACCEPTED BY 
DEPUTY MINISTER, ENERGY ON GROUNDS THAT 
INSUFFICIENT EVIDENCE TO SUPPORT BAN. 

MOE AND MTC CHARGED TO RESOLVE DILEMMA, 



42 



/LC..[.[.QNjAjsr-N iiY. f«!_ 8 n'lr, 



1977 - L.S, LOVi:. SlUDY fiimiSSliJNLn \im 

FUNDING TilRnUGH LOT! TRY PROGRAf-^ 

1978 - L,S, LOVE SIUDY CONIINUES DUE TO POOR 

RESULTS IN 1977 



MAY 1979 



LOVE REPORT FINALIZED AND 
SUBMITTED TO MOE, 



43 



C ONTINUING ACTION RY TASK FORCF 



1971 OEElIJiJillJi^ADJiLERS. ASSOC:, 

- ROAD OILING IN USE AND ENDORSED BY TOWNSHIPS 
FOR OVER ''0 YEARS 

- CALCIUM CHLORIDE NOT COfiPLETE SUBSTITUTE 

AND IS MONOPOLY IN ONTARIO AS ONLY ONE SOURCE 

- 71 PERSONS PLUS SEASONAL HELP DEPEND 
ON ROAD OILING FOR LIVELY HOOD 

- HHAT WOULD HAPPEN TO 8 MILLION GALS. 
OF OIL CURRENTLY USED FOR ROAD OILING 

- NO SCI ENTIFIC EVIDENCE TO INDICATE ROAD 
OILING UNACCEPTABLE. 

- NOT ALL WASTE OIL CAN BE REREFINED AS 
SOME OF VEGETABLE AND ANIMAL ORIGIN 

- SPECIFICATIONS SHOULD BE DEVELOPED BY MOE 
MTC AND MNR TO REGULATE OPERATORS, QUANTITY 
AND QUALITY OF OR USED AND METHOD OF 
APPLICATION 



44 



CnNT lNUING ._AXIiON_iY_I.ASl_F0R£R 

SUMMER. 1979 MEETING WITH WASTF O IL REF INFR 

BRESLUBF 

- NEED TO CONSERVE PETROLEUM RESOURCES 

- NEED TO PROTECT ENVIRONMENT 

- BAN ROAD OILING 

BRESLUBE OPFRATinKI^; 

- CURRENTLY. 2-5 MILLIONS GALLONS PER YEAR 

- ABOUT 1 MILLION IMPORTED FROM OIIEBEC. ILS 

- EXPANSION UNDERWAY 

- 5-0 MILLION GALLONS BY FALL IV^ 
' 10 MILLION GALLONS 3Y MID 1980 
I.E. CAN HANDLE ALL WASTE OIL 



zm m bJVddi:; no ]Ei oi my i^iiiMH 



aasodoiid 3^ 110 TvTJ3dwi iiiin SNoissnosia (? 



lU 



0861 3iV1 Wl iJViyiS NO IH 0! 
SSBDOiJd OKiUWiJiOyQAll SdlTlIlld 3111 ISR GIHOf 



OiNOb'Oi m AfJ3NlJ3y3;'l 
md IVSOdOlld VQVNVD 313I1S (T B'ZSt^HlS 



sj.iivss3yddns isna 

3AIlWMy3.nV flO fJOIiVlJ^'0,.INI aiOIAOyd S9fJI133W 3S3II! 

3iVNOiid3nsoM3n ynioivD ~ y3znims avo^j 3« 

S1V:)I[J31D dSW H.LIH 9N1L131! {£ 

,X3y3110'J, 31' 
1V0IW3HJ OjiIM Hiirt DlJli:i3W (c 

30 1 y 01 H J i-illlDlVD 3H 
1V01W11I1 QIIIIV ILIM 9N!.N-!;j (T (SZETT3M;!nS 



Ulllil 1SVI A'.i iMiMllV 'iMliif^Til).) 



46 



CONTINUING A CTinN RY TA9^Fnp££ 

MAY 1980 MOE REPORT ON EFFECTS OF ROAD 

OILING ON PCB ACCUMULATION IN AQUATIC LIFE 



STRONG CIRCUnSTANTIAL EVIDENCE THAT PCB 
IN ROAD OIL IS PICKED UP BY FISli 
MAY BE RESPONSIBLE FOR PCB'S FOUND 
IN RESORT .AREAS LAKES 



ACTION B Y MOF 

APRIL 1978 'INTERIM GUIDELINES RESPECTING 
PCB IN WASTE OILS' 



ROAD OILING 25ppm MAX 

FUEL FORCEMENT KILNS IOOppm MAX 
FOR REREFINING 25ppm MAX 



47 

WHERE DO THINGS NOK' STAND? 

- CONCERNS OVER ROAD OILIIJG PRACTICES 

- LEAD 

'^^^^ - HEALTH 

-HEAVY METALS _ ENVIRONMENT 

- PCB 

- POSITIONS PRESENTED BOTH FOR AND AGAINST 
ROAD OILING 

- SUBSTITUTES FOR WASTE OIL NOT AVAILABLE FOR 
ALL CASES 

- NO WELL DEFINED HEALTH OR ENVIRONMENTAL 
IMPACTS BUT STRONG CIRCUMSTANTIAL EVIDENCE 

- ADDITIONAL REREFINING CAPACITY TO BE AVAILABLE 
WHICH WILL COMPETE FOR WASTE OIL 

- PUBLIC PRESSURES FOR BAJJ FOLLOWING BAN BY US. EPA 



mnu OILERS NEED LEAD TINE OF APPROX 1 YEAR AS OIL 
ACCUMULATED OVER WINTER FOR NEXT SEASON 

- SOME MUNICIPALITIES EXPRESSED CONCERN OVER PROPOSED BAN 
DUE TO INCREASED COST AND NON-AVAIU\BILITY OF SUBSTITUTES 

- ST, LAWRENCE CEMENT NO LONGER ACCEPTING WASTE OIL AS FUEL 

- REGULATION ON MOVEMENT OF PCB'S 



48 



yiiAI_IS. PLANNED? 



WASTE OIL TASliOR££ WILL CONCLUDE ITS DELIBERATIONS 
SHORTLY AND RECOMMEND; 

1) MOE TO RESOLVE ROAD OILING POLICY 

2) WASTE OIL UTILIZAITON NO LONGER A 
CONCERN DUE TO REREFINERY PROPOSALS 



MOE POLICY? 

1) CONSIDER SPECIFICATIONS ON WASTE OIL TO BE 
USED FOR ROAD OILING. 

- PCB 

- LEAD 

- VANADIUM 

2) CONSIDER GUIDELINES ON APPLICATION 

- MAX, APPLICATION RATES 

- PROXIMITY TO WATER BODIES 

3) CONSIDER RAMIFICATIONS OF SURVEILLANCE 

- MANPOWER RESOURCES 

- FINANCIAL RESOURCES 

i|) CONSIDER ANALYTICAL REQUIREMENTS AND CAPABILITIES 

WHEN? 

EARLY 1980 



m 



BIOACCUMULATION RATES, ACUTE AND 
CHRONIC EFFECTS OF NEW DIELECTRIC 
FLUID PRODUCTS ON FISH 



SUMMARY REPORT FOR 

PROVINCIAL LOTTERY PROJECT NO. 77-003-32 

1977 - 1980 



by 

GEORGE W. OZBURN, 
ALASDAIR D. SMITH 
DONALD E. ORR 

LAKEHEAD UNIVERSITY 
THUNDER BAY, ONTARIO 

November 1980 



50 



BIOACCUMULATION RATES, ACUTE AND CHRONIC 
EFFECTS OF NEW DIELECTRIC FLUID PRODUCTS ON FISH 



SUMMARY REPORT 
FOR 

PROVINCIAL LOTTERY PROJECT NO. 77-003-32 
1977 - 1980 



b y 



GEORGE W. OZBURN, PROFESSOR, DEPARTMENT OF BIOLOGY 
ALASDAIR D. SMITH, RESEARC, ASSOCIATE, DEPARTMENT OF BIOLOGY 

AND 
DONALD E. ORR, ASSOCIATE PROFESSOR, DEPARTMENT OF CHEMISTRY. 



LAKEHEAD UNIVERSITY 



THUNDER BAY, ONTARIO 



NOVEMBER, I98O. 



I 



TABLE OF CONTENTS 



INTRODUCTION t 

DIELECTRIC FLUIDS 2 

ANALYTICAL MEASUREMENT 6 

CHEMICAL DATA )2 

ACUTE TOXIC ITy 1 7 

REPRODUCTIVE EFFECTS 21 

BIOCONCENTRATION: WATER EXPOSURE 25 

BIOACCUMULATION: UPTAKE VIA FOOD 30 

SUMMARY 5f 

BIBLIOGRAPHY 37 



31 



52 



INTRODUCTION 

In 1971, North American sales of polychlorlnated by- 
phenyls (PCBs) were restricted to sealed electrical equipment 
in an attempt to reduce environmental contamination by these 
residue-forming compounds. Despite this restriction, U. S. 
air and water monitoring programs carried out between 1971 
and 1976 had not detected any decrease in PCB levels. (Walker, 
1976). It soon became apparent that even the use of PCBs as 
dielectric fluids would have to be curtailed if acceptable en- 
vironmental backgrounds were to be realized. Manufacturers of 
dielectric fluids were quick to realize this fact and by the 
mid-seventies several companies were promoting new chemicals 
as PCB- alternatives for use in transformers and capacitors. 

Suitable PC B-s ubs t i tu tes not only had to possess favor- 
able dielectric properties, but also had to be environmentally 
acceptable. The chemical manufacturers did indeed conduct "in 
house" toxicolog ica 1 studies of their proposed P C B - rep 1 acemen t 
chemicals. The data derived from these studies were incorpor- 
ated into brochures designed to promote the sale of these pro- 
ducts. In the scientific literature, however, little or no 
tox i CO 1 og I ca 1 data on these chemicals existed. 

Re cog n izing the need for an impartial and comparative 
investigation on the environmental compa tab i 1 i t y of these new 



53 



dielectric fluids, the Aquatic Research (-roup at Lakehead 
University submitted a proposal in 1976 to the Ontario 
Ministry of the Environment to conduct an aquatic toxicity 
study of several of these new products. The proposal was 
accepted by the Ministry and the study commenced on May 1, 

1977. 

Although the original proposal called for a study of 
five PC B - 5 ubs t I t u tes , only four were evaluated during the 
three-year period of the study. We had anticipated that 
reliable analytical methods for these exotic chemicals would 
be available, either In the scientific literature or from the 
manufacturers. On the contrary, it was discovered that ana- 
lytical procedures for extraction and quantification were 
cither poorly documented or virtually non- ex i s t an t . Conse- 
quently, much of the analytical support had to be developed 
by our own group during the course of the study. In retro- 
spect, a more realistic proposal in terms of the available man 
power would have called for an evaluation of only three PCB- 
substitutes within the specified time period of this study. 



DtELE''TRIC FLUIDS 

The dielectric fluids were chosen in consultation with 
Ministry of the Environment and Ontario Hydro personnel. It 
was decided that the compounds Investigated would be those 



54 



that had met the electrical requirements of Hydro and were, 
therefore, serious contenders as PCB- rep 1 acemen ts In the 
Province of Ontario. 

The chosen chemtcais were trlchloro benzene, polydime- 
thy Is i loxane , butyiated monoch iorod i pheny I oxide and isopropyl 
biphenyl. The PCB, Aroclor 1016, was also chosen as a "bench- 
mark" chemical. Analytical methods for PCBs are well esta- 
blished and the scientific literature is well documented with 
respect to tox i co 1 og i ca I effects of PCBs on fishes. Initial 
work with A. 1016, therefore, gave our research group valuable 
experience in working with hydrophobic chemicals. It also 
served as a basis for either developing or improving analytica 
techniques for the new dielectric fluids and as a reference 
compound to compare the environmental suitability of the pro- 
posed replacement chemicals. 

1 . Aroclor 1016 (PCB) 

Aroclor 1016 is a capacitor fluid manufactured by 
Monsanto Chemical Company. It. Is a po 1 y ch I o r i na ted biphenyl 
(PCB) consisting of a mixture of 56^ t r i ch 1 or i na ted biphenyl, 
2U di - and te t rach 1 o r i na ted biphenyl and less than t^ of 
mono - and pentachlorinated biphenyl. Fig. 1 is the 
structural formula for A. 1016. 



CI 




x+y=l, 2, 3, A,5 



Fig. I. Structural formula for Aroclor 1016 



^ 



55 



2. Polydimethyls i loxane (PDHS) 

D i methy I s i 1 oxane is the basic chemical unit comprising 
a series of silicone products manufactured by Dow Corning 
Corporation. Dielectrics in this series are collectively re- 
ferred to as Dow Corning 200 fluids. These liquid silicones 
are po I y d i me t hy 1 s i 1 oxanes ( POMS ) , where the repeating polymeric 
unit (dimethylsiloxane) can be as high as 10, 000. In the case 
of our sample, Dow Corning 561 trans former fluid, the actual 
degree of polymerization was unknown. Fig. 2 is the structural 
formula for the 200 series of Dow Corning silicone fluids. 



CH 



HO— Si— 



CH 



CH3 




Si— 





CH3 





CH 



Si— OH 



CH 



-"X 



Range of x:0 to 10,000 



Fig. 2. Structural formula for Dow Corning 200 fluid 



3. Tr i ch 1 orobenzene (TCB) 

Trichlorobenzene (TCB) is a common organic compound which 
exists in three isomeric forms: 1, 2, 3 - TCB; 1, 2, k - TCB; 
and, 1, 3, 5 - TCB. Under normal conditions, the 1, 2, 3 
and 1,2,^- isomers are liquids whereas 1, 3, 5 - TCB is a 



56 



solid. The trrchlorobenzenes possess favourable dielectric 
properties and General Electric Corporation markets a tech- 
nical grade mixture of 331 i, 2. 3 - and 66% ], 2, A - TCB 
as a transformer fluid. In the Province of Ontario, technic- 
al grade TCB has been used to "top up" existing PCB - filled 
tranformers. Fig. 3 is the structural formula for TCB 




1 some rs : 




U2,3 


- TCB 


1,2,/. 


- TCB 


1.3,5 


- TCB 



fig. 3. Structural formula for Trichloro benzene 
k. Monochl oromonobutyl d i phenyl oxide (^^ClD PO^ ^ 

The Dow Chemical Company manufactures and markets a 
capacitor fluid under the trade name, Dow Dielectric Fluid C^t. 
The major component of C4 fluid is monoch 1 oromonobuty I di pheny 1 
oxide (C^ciDPO) , with lesser amounts of monoch 1 orod i pheny I 
oxide and monoch 1 orod i buty 1 d i pheny 1 oxide. Smaller amounts of 
monochlorotrlbutyldiphenyl oxide (<5^) are also present. The 
actual percentage of these compounds in the capacitor fluid 
is unknown. Our sample consisted of the major component of 
C4 fluid, C^CIDPO, with trace amounts of CIDPO present. Fig. k 
is the structural formula for C.CIDPO 



57 



I 
II 
II 




CaH 



4n9 



Fig. '^ . Structural formula for Monochloromonobutyld iphenyl oxide 

5. I sopropy I b i pheny I (IPB). 

Westinghouse Electric Corporation markets a capacitor 
fluid under the trade name, Womcol. Chemically, Wemcol is 
i sopropy I b iphenyl (IPB). Although Wemcol is advertised as 
lOO^S IPB, we found our sample to contain up to 1^ di-!sopro- 
pylbiphenyl. Fig. 5 is the general structural formutz for 

(C,H7) 




(C5H7) 



ANALYTICAL MEASUREMENT 



1 . Acetone (C-H^CO) 



Acetone is widely used as a dispersant or carrier solvent 
for introducing hydrophobic chemicals into aquatic bioassay 

systems. We used acetone as the dispersing agent in the present 
study and hence a method for the analytical measurement of 
acetone in water was needed. 



58 



We employed a colorimetric method involving the pro- 
duction of dinitrophenylhydrazones from 2, /* - d i n i t ropheny I - 
hydrazine in the presence of ketones (British Drug House. 
Limited, 1974). Although acetone is thoroughly soluble in 
water, its' chemical Instability and high volatility results 
in measured quantities of approximately 80^ of the nominal 
concen t ra t ion . 

Dow Coming's 561 transformer fluid was originally de- 
signated as the first PC B- s ubs t i t ute to be studied. Work be- 
gan in early May. 1977, to develop an analytical method for re- 
covery and measurement of po 1 y d i me thy I s i 1 oxane (PDMS) in water. 
No convenient method existed in the scientific literature. How- 
ever, a method for the determination of PDMS in beer and yeast 
by infrared spectroscopy was available (Sinclair and Hallam. I971) 
Numerous problems were encountered trying to adapt this method to 
water analysis. PDMS was found to be virtually insoluble in water 
In order to obtain measurable amounts of PDMS in water, concentra- 
tions of 50.000 mg of acetone per litre were required. An acetone 
concentration of this magnitude Is lethal to fish, being more than 
six times greater than the LC^ value.. 

The low solubility problem was further complicated by the high affi- 
nity of PDMS for glass. Reproducible extractions were rarely obtained due 
to adherence of the silicone product to the analytical glassware. Consider- 
able time was spent trying to rid the glassware of silicone contamination. 



4 



I 



59 



I 
I 
I 



We found that a combination of multiple washings with 
ether and oven annealing at 570° C was the only effective method for 
removir.g PDMS from glass. This procedure, of course, could 
not be used to clean the bioassay system. If PDMS was to be 
studied first, the diluter and test tank system would have 
to be discarded and rebuilt. After discussions with MOE 
personnel, It was decided that the technical problems were 
too great to solve within the time period allotted for this 
chemi ca 1. PDMS , therefore, was placed at the end of the list. 
If time permitted we would return to the study of PDMS after 
completing our investigations of the other dielectric fluids. 

3. A. 1016, TCB, C, CIDPO , and IPB 



The remaining chemicals were all amenable to analytical 
measurement by gas chroma tography. 

A Hewlett-Packard 5730A gas ch roma tog raph equipped with 
both electron capture (ECO) and flame ionization (FID) dectec- 
tion modes was purchased as an instrument dedicated solely to the 
dielectric fluids project. Table I summarizes the gas chroma- 
Lographic (GC) conditions employed for the analytical measure- 
ment of the remaining four dielectric fluids. 

A. 1016 was not included in the original proposal. It was 
added to the Irst as a reference chemical at the request of 
Dow Chemical personnel. The rational was that the inclusion 



TABLE I. GAS CHROMATOGRAPHIC CO\-DITION'.S FOR ANALYTICAL MEASUREMENT ^ 



DIELECTRIC 

FLUID 
A>:ALY2ED 


COLUN^M PACKING 
SUPPORT BWSE 


DETECTOR USED 
FOR 
.V^ALYSIS 


DETECTOR/ 
I>iTECTOR 
TEMP. (°C) 


CARRIER 
GAS/PRESSURE 
(PSI) 


CARRIER 
GAS FLOW 

(Mi/Ml N) 


CC^IPONENT 

RETENTION TIMES 

(MINUTES ANT) SECONDS) 


\.1016 


Z% QF-1, 
31 DC-200, 

ON GASOiRai Q 


ECD 


300/250 


5^ ARCAN' 
IN 

MbI!WNE/60 


50 


aiLORO, 7:20 

DIQILORO. 9:20 

TRICHLORO. 12:00 
TFTRACHLORO. 14:20 

°ENTACHLORO. ^^'^^ 


rcB 


8% BENTONE-54, 

10^<, l)C-300, 
ON GASCHPOM Q 


ECD 


3b0/250 


S% ARGOU 

IN 

f^ETTIANE/fiO 


50 


1, 2, 4-TCB 2:10 
1. 2, 3-TCB 5:00 


:4CXDP0 


SI aav-98 

ON GASaiRQM Q 


FID 


300/150 


N^GO 


40 


c/dPO 7:30 
C^ClDPO 8:25 




31 OV-210, 
ON aiRDM. W 


FID 


300/150 


N /60 
2 


25 


MONO-IPB 9:00 
DI-IPB 9:36 



a) INSTRUMENT: HEWLETT-PACKARD, MODEL 5730A 



o 



I 



61 



of a dielectric fluid with established analytical procedures 
and well documented biological effects would serve as a 
"quality control" check on the methods used to generate both 
chemical and biological data on the PCB-s ubs t i t utes . We 
were pleased that the Dow people insisted on the inclusion of 
A. 1016 as a benchmark chemical. The i^ey to good analytical 
bacl<up for bioassay studies of hydrophobic compounds depends 
heavily upon the efficiency with which these compounds can be 
recovered from water and tissue samples. Dow provided us with 
excellent extraction methods for PCBs and this information 
served as a basis for the development of efficient extraction 
procedures for TCB, C.CIDPO and IPS. 

The extracting solvent was hexane, rather than ether 
which was suggested in the original Dow method for PCBs. Our 
studies indicated that both solvents were equally efficient in 
extracting the PCB-s ubs t I tutes from water. Hexane had the 
advantages of being cheaper and less hazardous than ether. 

The following general outline summarizes the procedure 
employed for extracting TCB, C^ClDPO and I PB from water. In 
ail cases, the water sample size was 250 ml. The volume of 
hexane varied slightly, however, depending upon concentration 
and ease of extraction: 



A 250 ml sample of water was tal<en from the midpoint of 
the test lank. Care was taken not to include any sur- 
face water or bottom sediment. 



62 



b) The sample was placed in a 500 ml separatory funnel and 
a predetermined vol ume of hexane was added. 

c) The funnel was shaken at maximum speed on a mechanical 
shaker for 20 minutes. 

d) The water/hexane mixture was allowed to separate and 
the hexane phase (containing the dielectric fluid) was 
tapped off. 

®' '' necessary, the hexane extract was concentrated by 
reducing the volume by evaporation over a hot water 
bath . 

Extraction of dielectric fluids from fish tissues was 
somewhat more complicated. Again, our method was a modified 
version of the Dow procedure for PCBs: 

a) A whole fish was placed in 20^^ methanolic KOH at 50°C 
for 20 minutes. 

b) The resulting digest was extracted with a predetermined 
volume of hexane in a separatory funnel by mechanical 
shak i ng . 

c) The hexane extract (containing the dielectric fluid and 
lipid material) was allowed to separate from the caustic 
solution for 15 min.tes. 

d) The extract was tapped off and dried over Na«SO, 

2 i* 



-i 



I 

I 
I 

I 



63 



e) The extract was then evaporated over a hot water bath 
to 2 ml, applied to a Florisil column and eluted with 
. S% ether i n hexane . 

The resulting hexane extracts from both water and tissue 
samples were injected directly into the GC . Standard curves 
were developed for each dielectric fluid by injecting hexane 
standards containing known concentrations of the chemical. 
Extraction efficiencies from both water and tissue were deter- 
mined by spiking clean samples with known concentrations of 
dielectric fluid and comparing the GC response to the standard 
curve. In cases where the extraction efficiency was less than 
100^, correction factors were calculated and used to adjust the 
measured concen t rat I on. By varying the volume of hexane, an opti- 
mum extraction efficiency could be obtained for each dielectric 
fluid. This enabled us to keep correction factors as small as 
possible when it was necessary to use them. 

When concentration of the GC sample was necessary, tests 
were done to ensure that no significant loss of dielectric fluid 
occurred during evaporation of the hexane extract. 

CHEMICAL DATA 
1 . Water Solubility . 

The scientific literature contains numerous methods for 



6A 



determining the solubility of hydrophobic organic compounds 
in water. The problem is that no two methods will yield the 
same result. According to the ASTM, no acceptable standard 
method exists. Although this is perhaps a problem for the 
chemists to sol ve, aqua t i c tox i co log J s t s must at least try to 
address it. It is not unusual to see published papers on 
aquatic bioassay studies of hydrophobic chemicals In which the 
author attempts to hide the solubility problem in a mass of 
biological data or ignore it completely. Our experience with 
the dielectric fluids study has convinced us how critically 
important a reliable method for water solubility is in generating 
meaningful bioassay results. 

Our attempts to develop a useful relevant method for deter- 
mining water solubility have been presented in detail in a re- 
cent publication (Todd et al . . 1979). The following general 
outline summarizes our method of choice, which we thinly most 
closely approximates the phy s i ca 1 /chem i ca 1 conditions in our 
flow -through bioassay systems: 

a) 500 ml of distilled water is super-saturated with the 
hydrophobic chemical and stirred at medium speed on a 
magnetic stirrer for 24 hours. 

b) eight, 50 ml aliquots of water are removed and centri- 
fuged at 15,000 rpm and 1 8°C for 90 minutes. 



I 



65 



c) 25 ml of supernatant is removed from each centrifuge tube. 

d) two sets of four, 25 ml samples are combined to give two, 
1 00 ml samp I es . 

e) the samples are then extracted once with 30 ml of hexane, 
and once with 20 ml of hexane; both extractions use a 2- 
minute, mechanical shake. 

f) the hexane extracts are then concentrated to 1 ml and 

injected into the GC. 

Table 2, entitled "Chemical Data", summarizes our solubility 

values for TCB, C.CIDPO and I PB using the above method. Other solu- 
bility figures, extracted from the scientific literature, have been 
included for comparison. It is readily apparent that there is 

tremendous variation in these data. It is not surprising, there- 
fore, that similar variations in biological responses are re- 
ported by different investigators studying the same hydrophobic 
chem i ca 1 s . 

2. Qctanol/Water Partition Coefficient . 

Table 2 also summarizes the octanol/water partition co- 
efficients determined in our laboratory for TCB, C.ClDPO and 
IPB. Again, values extracted from the literature have been 
included for comparison. 

The octanol/water partition coefficient (log P) is an 
important parameter for predicting the biological effects of 
organic chemicals from physical properties through the use of 
structure - activity correlations {Veith and Konasewich, 1975). 



TABLE 2. 



C H EfllCAL DATA 



DiFLFCTRIC 


Solubility 


o/w PT 


Source 


A, 1015 


0.05i< 


- 


Branson^ 1977. 




0.100 


- 


flERCIER. 1977. 




- 


5.9 


VeITH EI ALw 1979. 


PDMS 


INSOLUBLE 


- 


RowE^ Spencer^ Bass^ 1948. 


TCB 


0,^78 


4.7 






- 


i).2 


Veith EI AL.. 1979. 


CijClDPO 


0.026 


1.7 






O.WO 


1.2 


Branson^ 1977. 


IPS 


0.051 


7.0 






10.0 


- 


riERCIER. 1977. 




- 


1.6 


Kenaga, 1980. 














I 



67 



I 
I 



Use of the log P value for estimating the b ioconcen t rat I on 
potential of organlcs In fish has been demonstrated by Neely 
11 aj.' ► (197^)- We determined log P values simply as a check 
on the validity of our b ioconcen t rat ion data, particularly our 
calculations for b ioconcen t rat ion factor (BCF). 

Although there are sophisticated methods such as high 
pressure liquid chroma tog raphy (HPLC) for measuring log P 
(Veith e_t_ a±. , 1979), we used the following classical method: 

a) weighed out into four, 50 ml volumetric flasks, 
500 mg lots of dielectric fluid. 

b) filled flasks to 50 ml mark with purified n-octanol. 

c) shook each 50 ml lot with 200 ml of water for 15 
minutes on a mechanical shaker at medium speed. 

d) trans ferred ^0 ml of water to each of 2 centrifuge 
tubes and centrifuged for 90 minutes at 5°C and 
12,000 rpm (8 tubes, total). 

e) took 25 ml samples of the water from each tube and 
combined two, 25 ml samples to give 50 ml. 

f) extracted the 50 ml samples with 20 ml of pure hexane 
for 5 minutes (mechanical shake). 

g) concentrated the hexane to I ml and injected into the 
GC . 

Log P is calculated as the ratio of the concentration of 
the chemical In the octanol to the concentration in the water. 



68 



Chemicals with large values for log P have greater bioconcen- 
tration potential and thus greater BCFs than those with small 
log P values. From Table 2, our determinations of log P in- 
dicate that iPB has the largest value and should yield the 
largest BCF In a b I oconcen t rat ion test. TCB and C.CIOPO have 
similar log P values and hence, should have similar BCFs. The 
BCF for A. 1016 should be less than that of IPB but greater 
than TCB and C. CI DPO. 

ACUTE TOXICITY 

Standard 96-hour flow- through toxicity tests were con- 
ducted according to the methods described by the Committee on 
Methods for Toxicity Tests with Aquatic Organisms (1975). The 
flow-through system has been previously described (Smith et al., 
1977). American flagflsh {jordanetla floridae) were used as 
the test species and tests were conducted on both adults and 
fry. Water temperatures were maintained at 25" l°C and dis- 
solved oxygen levels were kept above 6.9 mg/1 at all times. 

Nominal chemical concentrations conformed with a recom- 
mended concentration series (Sprague, 1973). The chemicals 
were introduced at least 2^ hours before adding the fish. 
Water samp les {250 ml) were analyzed for actual (measured) 
chemical concentration prior to int roducinq the fish and every 
2k hours thereafter, throughout the duration of the test (i.e. 
N«5). Data were analyzed by computer , utilizing an LC^ pro- 
gram developed by Stephan (1977). The program subjects the 



-I 



I 

I 

I 

I 
I 

B 

I 
I 

« 



69 



I 

I 
I 
I 
I 
I 
I 
I 
I 
t 



concentration/mortality data to a series of progressively 
more sophisticated statistical tests: 1) a simple bi- 
nomial test; 2) the moving average test; and, 3) the probit 
analysis (if the concentration gradient tested produces at least 
two partial kills). The probit analysis, of course, is the most 
powerful teiit and hence yields the best estimate for the LCr-f^- 
Sicphan's computer program is entirely based on criteria esta- 
blished by the Commi ttee on Methods for Toxicity Tests with 
Aquatic Organisms (1975) and hence, is compa t ible with the 
t.'bt methodology which we employed. 

i . Ace tone 

No LCrQ value for acetone against our test species, flag- 
fish, could be found in the literature. It was there fore, 
necessary to establish the acute toxicity of the dispersing 
agent in order to determine what concentrations could be safely 
used to introduce the dielectrics into the test system. Our 
estimates of the LCrQ for acetone (Table 3) agree well with the 
value reported for b 1 ueg i 1 I s (Cairns and Scheier, 1968). 

On the basis of these tests, we initially chose an acetone 
carrier concentration of 79 mg/l (100 y]/]) which is less than 
I <, of the LCcQ estimate. However, the dielectric fluids exhi- 
bited such poor water solubility that we increased the carrier 
concentration to 1 96 mg/l. This concentration is equivalent 
to 2.3s of the l^rr. value. 



70 



2. Die ] ect r i c Fluids 

Table 3 compares the acute toxicity of the dielectric 
fluids we Investigated. Where no acute data on a particular 
fluid was generated, literature values have been Included. 
Table 3 also compares our data to that of other investigators 
who have determined LC^^ values for some of these dielectrics. 

Great care must be taken in the interpretation of the 
data presented in Table 3- The test method (i.e. static or 
flow-through), the species and age of the fish, and the water 
temperature are all important factors which contribute to the 
observed biological response (I.e. mortal Ity). Perhaps the 
most important factor, however, Is the water solubility of the 
chemical. Nearly all of the LC^q values listed In Table 3 are 
greater than the reported solubilities (Table 2). 

The classic acute toxicity test assumes that the toxic 
substance is in true solution. In the case of hydrophobic 
chemicals like dielectric fluids, solutions above the satura- 
tion point are usually involved. Mortality, therefore, is not 
only a function of the dissolved portion of the chemical but 
^Iso of the undissolved phase. This is probably the reason 
why reported LC^^ values for hydrophobic chemicals often vary 
considerably from one laboratory to another. 



CHEMICAL 


TABLE 3- 


ACUTE 


96-HOIJR LC^ I'm 


%U ) '^ 


i SOURCE 




FISH 


T f 
^^50 


951 C.L. 


1 METHOD 




ACETONE 


FLAGFISH: ADULTS 
FRY 


8,496 
7,659 


8,094-8,918 
6,989-8,392 


FLOW-TllROUG!! 








BLUEGUL ADULTS 


8.300 


- 


STATIC 


CAIR\S AND SCHEIER, 1968 


A. 1016 


FLAGFISH: ADULTS 
FRY 


0.05 
0.04 


0.04 - 0.07 
0.03 - 0.05 


FLOW-THROUGH 








FATHEAD ADULTS 


0.76 


0.58 - 1,02 


STATIC 


BRAN'SON, 19 7 7 




PDMS 


BLUEGILL ADULTS 


7-10,000 


- 


STATIC 


HOBBS^ £1 AL. 1975 


TCB 


FLAGFISH: ADULTS 
FRY 


3.18 
2.17 


2.88 - 3.51 
1.98 - 2.39 


FLOW -THROUGH 






C^CIDPO 


FLAGFISH: ADULTS 
FRY 


-7- 1.1^ 
0.67 


0.28 - 1.62 


FLOW-THROUGH 




IPB 


FLAGFISH: ADULTS 
FRY 


> 0.75 
0.28 


0.22 - 0.37 


FLOW-THROUGH 








BLUEFILL ADULTS 


4.00 


.,- 




MERCICR, 1977. 






TROUT FINGERLINGS 


2.50 


- 


STATIC 


II II 





CONCENTRATION OF ACETONE CARRIER 



196 mg/X ( 2.31 OF THE LC^^) 



72 



When the LC^^^ value for a hydrophobic chemical is 
within the same cojncen t ra t i on range as its water solubility, 
we can be reasonably confident that the LC^q is a valid 
number. For example, our LC^^ determined for A.l 1 6 (0.05 mg/ 1) 
falls well within the reported solubility range of 0.05^ to 
0.1 mg/I (Branson, 1977; Mercier, 1977). At the other end of 
the scale, the reported LC^q for TCB, 3-18 mg/ 1 , i i; approxi- 
mately six times greater than the reported solubility. It be- 
comes somewhat difficult, therefore, to interpret the useful- 
ness and perhaps even the relevance of an LC^q value such as 
that reported for TCB. 



50 



REPRODUCTIVE EFFECTS 

TCB, C^CIDPO and IPB were investigated with respect to 
their effects on reproduction in flagfish. 

Five-level, sublethal concentration gradients for indi- 
vidual dielectrics were established on the ba^^is of their LC 
values. With this exception, the testing protocol was identi- 
cal for all three chemicals. 

Juvenlie flagfish were randomly distributed among duplic- 
ate spawning tanks. Each tank received 15 fish. All fish were 
maintained in non-dosed, control water during a one-month growth 
and maturity period. 

Following maturation, the fish were selectively culled to 



73 



n r,3tfo of 5 fomalos to 1 moles pe. tank, and spawning sub- 
strates were introJuced. Once synchronous spawning in till 
test tanks was achieved, dielectric fluid addition was ini- 
t i a ted . 

The concentration of acetone carrier was 196 mg/1. 
Controls (water- and acetone) were included in each test. 
Stable choiiiicai concentrations were reached within the initial 
2A-hour dosing period. Water samples (2^0 ml) were analyzed 
^ days per week from alternate, duplicate tanks at each test 
ivvei. Ml i s sampling procedure and analysis continued through- 
out the duration of the test. 

Spawning substrates were removed daily and examined for 
eqgs. Clean substrates were immed iately substituted . Eggs 
were separated from the substrate and counted. Unfertile eggs 
and "shells" were discarded. A maximum of 50 viable eggs from 
each spawning wo re placed in individual egg cups. Cups were 
attached to a rocker arm ssembly and the eggs incubated in 
•heir respective progeny lanks. Excess eggs from water control 
were also Incubated at all test levels. Two hundred eggs per 
test level were used in this control transfer experiment. 
Following hatching of the control transfer eggs, 50 fry from 
each test level were transferred to the spawning tanks and held 
for fry survival testing. 

Differences in egg production and hatching success at 
different concentrations of dielectric fluid were tested for 



I 



74 



significance by a one-way Analysis of Variance. If a signi- 
ficant F-ratio was found, a Duncan multiple range test (Dun- 
can, 1955) was employed to determine which test concentrations 
yielded significantly different results. Fry survival was 
subjected to Chi-square analysl'^. 

Spawning periods ran for 21 consecutive days. Fry sur- 
vival was evaluated over 10-day periods. 

Measured concentrations of TCB were approximately 50% 
of the nominal concentrations; IPS and C^^t^lDPO averaged kO% 
and 30:, , respeci. ively. Measured concentrations, therefore, 
were in agreement with the order of solubility: TC B> I P B > C , C 1 DPO. 

No adult mortal ity occurred in the TCB and C.CIDPO tests 
during the spawning period {21-day exposure). However, adult 
mor tality did occut in the IPB test. Three fish died at 0.^2 
mg/1, I fish at 0.2 mg/ 1 and 1 fish at 0.1 mg/ 1 . 

Table k lists the important reproductive parameters and 
the thresh old concentrations for TCB, C.CIDPO and IPB at which 
these reptoductive stages were imp aired. 

'■'iClDPO had the mos t ove r a 1 1 detrimental effect on re- 
production in flagfish. Although TCB caused spawing impalr- 
nient at a lower concentration than IPB, fry were able to sur- 
vivi- higher concentrations of TCB than IPB. As expected, the 
egc) stage was nost resistant to al! three dielectrics. 



r 



DIELECTRIC 
FLUID 



TCB 



C^CiDPO 



IPB 



TABLE k. 



REPROnuCTI\T: rFFECTS 



THRESHOLD SPAWNING IMPAIRMENT 
IN" MG/i 



0.29 



0.0S4 



> 0.42 



THRESilOLD HATCHING IMPAIRMENT 
IN MG/j? 



1.71 



0.22 



> 0.47 



FRY SURVIVAL (10-day 
E)J>OSUREj IN MGM 



1 .4] 



0.023 



0.43 






76 



Again, water solubility must be considered in evaluating 
the effects of these dielectrics on fish reproduction. For 
TCB and C^CIDPO, spawning impairment was observed at concentra- 
tions within the same order of magnitude as the compounds ' solu- 
bility. IPB had no effect at concentrations 100 times greater 
than its solubility and hence, could be considered as the least 
detrimental to flagfish reproduction. 

BIOCONCENTRATION; WATER EXPOSURE 

Full-scale broconcentratton tests were conducted with TCB, 
C^CIDPO and IPB, but only the TCB and IPB tests were successful. 
A number of analytical problems resulted in a failure to generate 
useable bioconcentration data for C,C1DP0. These problems in- 
eluded: 1) poor GC sensitivity In the FID mode; 2) poor ex- 
traction efficiency from both water and tissue samples; and, 3) 
extremely low water solubility which made stable test concentra- 
tions over long periods of time almost impossible. 

The test protocol was in accordance with the Proposed 
Standard Practice for Measuring Bioconcentration of Chemicals with 
Fishes (American Society for Testing and Materials, 1978). 

Juvenile flagfish (approximately 6 months old) were random- 
ly distributed among six (3 duplicate) spawning tanks. Each 
tank received ^8 fish. One set of duplicates served as a con- 
trol , one set as the "low exposure" group, and one set as the 



I 



77 



"high exposure" group. 

Test fish were initially exposed to the dielectric fluid 
for a 28-day uptake period. During this uptake phase of the 
test, six fish (3 per duplicate tank) were sampled at both 
test levels (and control) for body burdens of dielectric after 
1, 3, 7, 1^. 21 and 28 days of exposure. Sacrificed fish were 
randomly selected and killed by over-dosing with MS-222. 

The remaining fish were transferred to a clean flow- 
through system for a 1^-day de [Duration period. During this 
phase of the test, six fish {three per duplicate tank) were 
sampled at both test levels (and control) for body burdens 
of dielectric after 1, 2, 3, ^, 5, 7, 10 and 1^ days. Again, 
fish were randomly selected and killed by over -dosing with 
MS-222. 

During uptake, water samples (250ml) we re taken daily 
(except week-ends and holidays) from all six tanks and analyzed 
for dielectric fluid concentration. In the TCB test, the low 
exposure averaged 1.5 yg/1 while the high exposure averaged 
9.6 ug/l. In the IPB test, average concentration levels were 3-5 Mg/1 
{low)and 2^1.1 pg/l (high). 

The concentration of acetone carrier In both tests was 90 mg/1. 

Data collected on water and tissue concentrations of 
dielectric fluid were analyzed by a computer program called 
Biofac. The program, developed by Dow Chemical Company, has 
been documented by Blau and Agin (1978). 



78 



Biofac utilizes esti mates of three important parameters 
derived from the ttme-concentration data: 1) the uptal^e rate 
constant, K^ ; 2) the clearance rate constant, K^ ; and, 3) 
the he teroscedast i c i ty parameter.^. The program then itera- 
tive I y searches for better values until the optimal values, 
Kj ; K^ and are found. From these optimal values, Biofac 
then calculates: 1) the b i oconcen t ra t ion factor (BCF); 2) 
the depuration half-concentration (T^); and, 3) the time re- 
quired to reach 90^ of steady state (T to 90^ S/S). 

Table 5 summar I zes our b i oconcen t ra t ion data for TCB and 
IPB. For comparison purposes, similar data on CrClDPO and 
tetrachlorobiphenyl (a component of A. 1016) have been in- 
cluded in the summary. Measured BCFs have been calculated by 
Biofac from real t i me- con cen t ra t i on data, F.stlmated BCFs have 
been calculated using the log P value (i.e. octanol /water par- 
tition coefficient). No information on the b i oconcen t ra t i on of 
PDMS could be found in the literature. 

An erroneous Biofac analysis for IPB was presented In an 
interim report on Wemcol (June, 198o). A programming error was 
discovered which resulted in a re-run of the Biofac analysis. 
The raw data was also sent to Dow Chemical for a Biofac analysis, 
to confirm our newly- generated data: 



TABLE i;. i^TocovcnMR.v. nv:; wajlu i:xi'osi-.ri: 



DIIILF.CTRIC 
i-LUID 


//g/d 



286 


abAR.A.\a: 
//s/d 

0.03 


DAY-s 10 i.u:i; 

STE.\DV ?T\-n": 


DAYS TO SO'^. 


BCF 
NOSW^iD ! ESTimiED 


SOURCP, OF 
REPERE\CE 


TCTRAaiL01^0BIPIIE>riT*a 


215.0 


_ 


9,550 




Branson, 1977 


TCB 


1,110 


1.21 


1.91 


0.5S 


92] 


1,755 


Veith et al., 1979 


c^cMk) 


142 


0.50 


4.65 


1.38 


292 


■■ 
756 


Blanchard et al, 1977 
Veitii et al., 1979 


IPB 


698 


0.24 


9.55 


2.SS 


2,896 


1,088 


Kenaga, 1980 



* a) 21^6 CO^fPOr^E^T of A.1016 






NEW BIOFAC ANALYSIS - I PB 



m 



PARAMtTER 

ME ASURED 
J. 

T^ 
BCF 

T to 90:^, S/S 



UNITS OF 
MEASU RE MENTS 

1/g/day 

, -1 

days 

days 
days 



LOW EXPOSURE 
(3.51 pg/1) 



HIGH EXPOSURE 
(2A.06 ug/1 ) 



698 


^61 I 


0.2^ 


0.'*3 


2.88 


1.61 


2896 


10790 


9.55 


5.32 


0. 388 


) .866 



Water concentrations used in the Biofac analyses reported 
in Table 5 were all in the 1 - 5 pg/l range. Similar exposure 
levels, therefore, render the data on all four dielectrics 
compa rab t e . 

The rates of uptake are in the order: TCB >IPB > tetra- 
chlorobiphenyl > C.CIDPO; clearance rates are in the order : 
TCB> C^C1DP0>IPB> tetrachlorobi phenyl. Although TCB exhib its 
the fastest b i ocon cen t ra t i on rate, it is also more rapidly ex- 
creted and/or metabolized than the other dielectric fluids. At 
the other end of the scale, the PCB (tetrachlorobiphenyl) exhi- 
bits both slow uptake and clearance. The times to 501 clearance 
for TCB, C^ClDPO and IPB were all within three days. Although 
this parameter is not reported for tetrachlorobiphenyl, the 
clearance rate constant for this PCB indicates that it would 
take 10-50 times longer for body burdens to be equivalently re- 
duced. 



81 



The PCB, of course, has the highest mea<jured BCF. Mea- 
sured BCFs for TCB and I PB wore about one order of magnitude 
lower. C^CIDPO Wc-js about two orders of magnitude lower than 
the PCB. Estimated BCFs (calculated from Jog P values) are 
in the same order of magnitude as those derived from real 
t i me- concen t rat i on data (i.e. measured BCFs). 



BIOACCUMULATIOM : UPTAKE VIA FOOD 
To compliment the water exposure tests with flagfish, 
wc applied a novel experimental approach to study the bio- 
accumulation dynamics in rainbow trout {Salmo gair>dner>i) fed 
diets containing PCB- s ubs t i t utes . Although this unique ex- 
perimental method was attempted with TCB, C.CIDPO amd IPB, 
only the TCB experiment was successful. Again, analytical 
problems with C^ClDPO and IPB were partly to blame for the 
failure of these experimenf^. Poor detection capability of 
the GC in FID mode forced us to use high concentrations of 
these dielectric fluids in the diet. This caused toxic effects 
on the fish, which in turn, disrupted their normal metabolic 
processes. Data was so sporadic that It was rendered useless. 
Another problem with the C^ClDPO and IPB experiments was the 
discovery of background residues (probably pesticides) tn both 
the trout stock and the comme re ial trout feed. These residues 
wore often present in such large amounts that they completely 



82 



ntaskod the dielectric fluid on the ch roma tog rams . 

These problems were not encountered in the TCB experi- 
ment. The mode of" detection employed for GC analysis of TCB 
is ECD, which has fur superior sensitivity. Also, no back- 
ground residues were detected. Thus, although residues were 
probably present in the TCB experiment as well, they did not 
cause interference In the GC analyses. The technique used 
in the TCB/food experiment was developed at the National Re- 
search Council of Canada. It involved the incorporation of 
a radioactive chemical marker, ^°^Hg - labeled methyl mercury 
in the diet. In addition to the chemical of interest (i.e. TCB) 

The rationale underlylnq the method has been discussed 
in detail by Gidiiey ct^ aj_. (I98O) and Roberts e_^ a_[ . (1977). 
In practice, a group of fish is given a single feeding or 
"pulse dose" of contaminated ration. A postdose series of 
whole-body gamma counts, obtained by the method of Ruohtula 
and MIettinen (1975), is then used to construct a curve of 
the asslmijation and clearance of the radioactive marker 
(Fig. 6). In Figure 6, the upper curve represents whole-body 
retention of the marker ( °^Hg) as a function of time. E Is 
the initial count obtained after the feeding of a single meal 
labeled with both marker and chemical of interest (i.e. TCB). 



83 




I 



£ 
c 



o 
o 

E 
a> 

o 



CP 

X 

ro 

O 

OJ 

c 
E 

(A 



TIME (days) 



Fig. 6. 



An illustration of two -compartment clearance of 

2 3 

Hg - labeled methyl mercury and its applica- 
tion in estimating the assimilation efficiency 
of any chemical of interest (modified from 
G Idney et al . , I 980) . 



g 
q: 

o 

CD 

UJ 

-J 
O 

i 



mn 



84 



Slope A represents clearance of the ingested dose of marker 
not absorbed from the gut tract. Slope B represents clear- 
ance of the marker sequestered in tissues, C Is obtained 
by extrapolation of Slope B and is an est! mate of the amount 
of marker sequestered in the tissues at zero time. The ratio 
C/E is an estimate of the net assimilation efficiency for the 
marker from the gut tract into the body tissues. 

The lower curve represents the ratio of the amount of 
TCB in the fish to the whole-body count as a function of time. 

2 Q -3 

The ratios are calculated from direct measurements of Hg 
and TCB determined on groups of fish sacrificed sequentially 
after voidance of the contaminated meal. D, obtained by ex- 
trapolation, is an estimate of the initial ratio. The net 
assimilation efficiency for TCB can be calculated from the 
initial ratio, D, the net assimilation efficiency of the Hg, 
C/E, and the actual ratio of TCB to Hg in the ration. 

The clearance of TCB from Individual fish Is calculated 
from the tissue concentration at the time of sacrifice and the 
estimated quantity initially sequestered in the tissues at 
zero t i me . 

The experiment employed a ration containing 50 ug/g of 
TCB. The assimilation efficiency and the percent of TCB cleared 
at several postdose times were then determined. 



H 



85 



Complete details of the TCB experiment have been pu- 
blished (Smith e^ aj_, , )98o). Table 6 summarizes the rele- 
vant data obtained in this study. Rainbow trout had an 
.issinillation efficiency fot^ TCB of 6l^. The data suggest 
that TCB is readily absorlird from the gut tract. However,. 
the trout were able to clear (i.e. excrete and/or metabolize) 
95^0 of the TCB body burden in less than 8 days. The esti- 
mated time to 50^ clearance was about k days. Thus, this 
data reflects the same pattern that was found in the water 
exposure experiment: TCB is both rapidly accumulated and 
rdpidly eliminated by fishes. 



TABLE 6. 



BIQACCUMULATION: UPTAKE VIA FOOD 



DIELECTRIC 
FLUID 



TCB 



TCB IK FOOD, 
ni^/g Cppm) 



50 



-ASSIMILATION 
EFFICIENa'/o 



61 



DAYS TO 95 "i CLEAR-WCE 
(MEASURED) 



7.25 



mVS TO SO?i CLEARANCE 
(ESTIMATED) 



3.82 



00 



SUMMARY 



87 



The Aquatic Research Group at Lakehead Universtty has 
qenerated some useful and unbiased information with res- 
pect to the PCB-bubstitute compounds studied: 

1. efficient extraction techniques for water and 
tissue samples, and optimum conditions for ana- 
lytical measure nient. 

2 . a preferred experimental method for determining 

water solubility. 

3. acute toxicity and reproductive effects, and whether 
or not these effects were within saturation levels 
(i.e. water solubility ranges). 

'^ . bioconcentration potential, determined from both 
physical/chemical correlations and actual water 
{and food) exposure tests. 



Bl BLIOGRAPHY 



American Society for Testing and Materials. I978. Proposed 
standard practice for measuring b i oconcen t rat i on of 
chemicals with fishes. ASTM - Draft No. 8. American 
Society fov Testing and Materials, Philadelphia (un- 
pub I i shed) . 

Blanchard, F. A,. I.T. Takahashr, H. C. Alexander and E. A. 

Bartlett. 1977- Uptake, clearance and b i oconcen t ra t ion 
of C - sec-butyl ~ k - ch 1 o rod i pheny I oxide in rain- 
bow trout. Aquatic Toxicology and Hazard Evaluation, 
ASTM STP 63^, F. L. Mayer and J. L. Hamelink, Eds., 
American Society for Testing and Materials^ Philadel- 
phia, pp. 162- 1 77. 

Blau, G. E. and G.L. Agin. I978. A User's Manual for Biofac: 

A computer program for characterizing the rates of uptake 
and clearance of chemicals in aquatic organisms. The Dov 

Chemical Companij, Midland. (Lab Report). 

Branson, D. R. 1977- A new capacitor fluid — A case study in 
product stewardship. Aquatic Toxicology and Hazard 
Evaluation, ASTM STP 63^, F. L. Mayer and J. L. Hamelink, 
Eds., American Society for Testing and Materials, 
Philadelphia, pp. AA-6I. 

British Drug House, Limited. 19^7. The BDH Book of Organic 
Reagents for Analytical Use. BDH Laboratory Chemicals 
Croup, Poole, Dorset, p . 56 . 

Cairns, J. and A. Scheier. 1 968 . A comparison of the toxicity 
of some common industrial waste components tested indi- 
vidually and combined. Pro.jve. Fish Cult. 30:3-8. 



89 



Ruohtula, M. and J. K. Micttinon. 1975. Retention and excretion 

o^ Hg - labeled methyl mercury in rainbow trout. Oikos^ 
26:385-390. 

Sinclair, A. and T. R. Hallam. I977. The determination of dime- 
thyl po I ys i 1 oxane in beer and yeast. Analyst, 96:l49-15i(. 

Smith. A. D., T. J. Griffith, D. E. r r , and G. W. Ozburn. 1 98O . 
Assimilation efficiency and clearance of t r i ch 1 orobenzene s 
in rainbow trout. Aquatic Toxicology, ASTM STP 707, J. G. 
Eaton, P. R. Parrish, and A. C. Hendricks, Eds. American 
iyooiety for Testing and Materials, Philadelphia, pp. 216-223 

Smith, A. D., J. R. Butler, and G. W. Ozburn. 1977- A penumatic 
dosing apparatus for flow-through bioassays. Water Res. 
1 1 :3W-3^9. 

Sprogue, J. B. 1973- The ABC's of pollutant bioassay using fish. 

Biological Methods for the Assessment of Water Quality, 

ASTM STP 528. J. Cairns Jr. and K. L. Dickson, Eds., 

Amcritnui y.ooietij for Tcstiwj and Materials, Philadelphia, 
pp. 6-30. 

Stephan, C. E. 1977. Methods for calculating an LC50. Aquatic 
Toxicology and Hazard Evaluation, ASTM STP 63^, F. L. 
Mayer and J. L. Name I i n k, E ds . American Society for Taatinfj 
and Materials, Philadelphia, pp. 65-8'4. 

Todd, J., D. E. Orr, and G. W. Ozburn. 1979- The unreliability 

of solubility data for organic compounds of low solubility 
in water. Proc. Sixch Annual Aquatic Toxicity Workshop, 
Winnipeg, November, 1979. Fisheries and Marine Service Tech- 
nical Report (in press). 

Vcith, G. D., D. L, Do Foe, and 8. V. Bergstedt. 1979- Measuring 
and estimating the b i oconcen t ra t i on factor of chemicals In 
fish. J . Fish, Res . Board Can. 36: 10^0-10^8. 



90 



Comm ittee on Methods for Toxicity Tests with Aquatic Organisms. 
1975- Methods for acute toxicity tests with fish, macro- 
invertebrates , and -mphibians. U. S. Environmental Pro- 
tection Afjency, Duluth. Eeologioal Research Series EPA- 
600/3-75-006. 

Duncan, 0. B. !955. Multiple range and multiple F-tests. 

Biometrics J 11:1 -k2 . 

Gidney, M. A. J., J. R. Roberts, and A. S. W. de Freitas. I98O. 
A technique for estimating individual ingested ration in 
group fed organisms. Environ, Soi, Techno I. (in press) . 

Hobbs, E. J., M. L. Kepiinger, and J. C. Calandra, 1975- 

Toxicity of po I yd i met hy 1 s i 1 oxanes in certain environmental 
sys tems . Environ, Res , 10:397-A06. 

Kenaga, E. E. I98O. Correlation of b I oconcen t ra t i on factors of 
chemicals in aquatic and terrestrial organisms with their 
physical and chemical properties. Am. Chem . Sac. 1^:553- 
556. 

Mercier, G. E. 1977. Wemcol capacitor fluid devei opmen t . 

Proc. Am. Power Conf. 39:10^3-1051. 

Neely, W. B., D.R. Branson, and G. E. Blau, 197^- Partition co- 
efficient to measure b I oconcen t r a t i on potential of organic 
chemicals in fish. Environ. Sci . Technol, 8:1113-1115. 

Roberts, J. R., A. S. W. de Freitas, and M. A. J. Grdney. 1977. 
Influence of lipid pool size on bloaccumulation of the 
insecticide chlordane by northern redhorse suckers 
( Moxostoma mac ro I ep I dot urn ) . J, Fish. Res. Board Can. 3^: 
89-97. 

Rowe , V. K., H. C. Spencer, and S. L. Bass. 19^*8. Toxicological 
studies on certain commercial silicones and hydrolyzable 
silane intermediates. J. Ind. Hyg. Toxicol, 30:332-352. 



Veith, G. D., N. M. Austin, and R. T. Morris. 1979. A rapid 
method for estimating log P for organic chemicals. 

Watci' Rcis. 13:^3-^7. 

Veith, G. D. and D. E. Konasewich. 1975. Structure-Activity 

Correlations in Studies of Toxicity and Broconcentration 
with Aquatic Organisms. International Joint Commission 
Publioation^ Windsor ^ Ontario. 

Walker, C. R. 1976. Po 1 ych 1 o r i n? ted biphenyl compounds (PCB's) 
and fisheries resources. Fisheries ^ 1:19-25. 



92 



FACTORS AFFECTING ACCUMULATION OF ORGANICS IN FISH 

G.R. CRAIG 
ONTARIO MINISTRY OF THE ENVIRONMENT 

LIMNOLOGY & TOXICITY SECTION 



ABSTRACT 



Historically, biological studies of organics have been 
limited to pesticides and PCB's. While these compounds continue 
to be monitored their importance has decreased as a result of 
controls effected voluntarily or through legislation. Pesticides 
however, will continue to be important in the study of other 
organic compounds due to the chemical/physical characteristics 
that they share. 

Pesticides were designed to optimize site specific 
activity, penetration of target organisms and environmental 
persistence. Consequently, the environmental effects have 
included slow degradation, wide spread dispersion, extensive 
biotic availability and unanticipated sublethal activity in 
non-target organisms. Additionally the analytical techniques 
for measurement of pesticides have been well developed allowing 
longer term evaluation. This analytical advantage is not always 
shared with industrial organics more recently identified in water, 
sediment and fish despite advances in gas chromatography and mass 
spectrometry. 

Greater attention is being paid to the structure of organics 
with respect to their biological activity. Chemical structure is 
being correlated with characteristics such as solubility, vapour 
pressure, polarity and octanol -water partition coefficients. 
Correlations between biological activity and the above chemical 
characteristics are being used to predict the activity of other 
organics identified in the environment but not yet studied in 
the laboratory. The logarithmic function of the octanol-water 
partition coefficient has been most useful in predicting acute 
toxicity of compounds to fish and invertebrates. Predicitive 
equations using the partition coefficient of compounds have also 
been developed to estimate the level of accumulation expected in 
exposured fish. 

The rates of organic accumulation and clearance 1n fish 
have been determined in the laboratory so that time to 90% 
saturation and the half life can be estimated. The presence of 
better documented pesticides or PCB's in field studies provides 
a reference for calculating accumulation rates of other compounds. 
Caged fish can be analysed periodically during exposure then 
transferred to an uncontaminated area and sampled during clearance 
to estimate the depuration rate. The ratio of accumulation over 
depuration rates represents the bio-concentration factor for the 
compounds identified. 



93 



Recognition for the need to assess or estimate 
the environmental hazard of the numerous organic compounds 
requires that a variety of predicitive techniques be 
developed. These techniques will unfold through further 
study of conventional organics and by selecting new study 
compounds according to measurable structure and physical/ 
chemical characteristics. Although predicting the bio- 
logical activity of organics does not substitute wholly 
for actual testing, the increasing resources and complex 
technology required to complete such assessments virtually 
prohibits emperical data generation for the many hundreds 
of compounds identified in receiving waters each year. 



9A 



THE PROBLEM OF ABANDONKn MXN1]S IN ONTARIO: 
A CONFRONTATION WITH HISTORY 



BY: J.E. iKJToNAN AND J.R. IIAWLIIV 

WASTH MANAGFM!:NT BRANCH 
ONTARIO MINISTRY OF TflE ENVIRONMENT 






I 
I 



95 



The ininmci industL-y in OniaLao has had a lor..; c\n.\ 
prosperous history. TLs l-oo1:s can bo Lfaood bad-: almost a 
century befiore Confederation, when, in 1770, Jesuit Fathers 
began experiment iny and working with native copper at 
Mamainse Point on the Rast short of hake Superior. 

Ontario's mining history up to the late 19'30's can be 
summarized as fol lows : 
L800 - I'lrst iron turnacr erected at r'urnace [■ais 

( Lyndhurst ) Lo..^.ls County 
1822 - l-'.rsL mining ci cvi-suin froin near Paris, Brant 

C o l; r" ■: y 
lti47 ~ First rri>ort*K: C".a-La'd:,!n oi-ei'irro:-c-"!? of Hranium 

Mineral -- m^:a rheano IVm ii I on -ast shore oi: Lake 
Superior 

llMij - Montrual Mining Company started mi'iing copper at 

Bruce Mines 
Ibby - First commercial .^il well in North America opened 

at Oil Springs, Lamb ton County 
.1866 - First discovery o'" gold at lUdorado, Hastings 

County ( Kichardson mine ) ^ 

High-grade silver discovered on island in Lake 

Superior (Silver Islet inine^ 

First production of salt near Godorich, Huron 
County 
iH7C - First commercxTl r^^hiomonts of ^ntite in c:dnada 
fro.. TJ<.rth nui,g. :,;■ Tow;-:!u,i^ h.-,nark County 
Fu-st shii-'inont of <;iraphit- i -om Nortii KLmsley 
j'ownship I/anark ■^■iini v 



-"tMi — -MM' ■■3..9..-'-3im«fM^^jiu^-- 'J ^'.yi y^.'jt 



96 



1878 ~ Gold discovererl .^t Laku of tho Woods 

1883 - Copper i.jfkel ore di sr.^vororl acar Sudbury {Murray 

mine ) 
1888 - First smelter blGJwn-i.P: ..Tt. "vionper CUtf 

Discovery oC natural q.'.s in Essex County 
1896 - Black Donald graphiire ini ne discovered, Renfrew 

County 

Talc mining started nonr Madoc, Hastings County 
1900 - Lake Superior Power Company commenced production 
from Helen iron mine at Wawa 

Corundum mining commenced Raglan Township Renfrew 

County 

1903 - lligh-grado cobalt-si 1 v. vr minerals discovered at 
Timiskaming 
Town of Cobalt named 

1905 - First r.:corded shipwntr of Canadian fluorite from 

Madoc, H,t'- tings C0m ,! ■- 

1906 - Silver di :^.:nvo ri.d :... -,r T.:>]:o„, qoU) discovarod at 

:ta;i:'tj;er l.aki^ 

First tU:^cuvory oF -FMri In Lho Porcupine area 
First discovrry of qol^l. at Kirkland Lake 
1916 - Falconbridge nickel dcpo.'^lts di:>covered at Sudbury 
1925 - Discovery of gold at Re<1 r.ake 
19J1 - Discovery of gold at Tiittlo l,on<j Lac 
1935 - Kir.st production of nenholi/ir^ syenit.o at Blue 

Mountain, Peterborounli f'ounty 
1938 - Discovery uf iron ore in l>od of steep Rock bake 



1908 
1911 



97 



1942 - First production of magnesium in Canada at Haley, 
Renfrew County 

1944 - Steep Rock Iron Mines commenced shipping of iron 

ore 

1945 - First production of calcium in Canada at Haley, 

Renfrew County 
1948 - Rediscovery of uranium at Theano Point, Lake 

Superior 
1950 - Discovery of Marmoraton iron-ore mine, Hastings 

County 

Production of asbestos commenced at Munro mine, 
Matheson 
1953 - International Nickel attains largest non-ferrous 
underground operation in the work at Sudbury 
Discovery of ore-grade uranium deposits at Blind 
River 

Discovery of copper-zinc at Manitouwadge 
1955 - First uranium ore produced Crom Blind River 

First contracts; for the sale of uranium from the 
Bancroft area 

First underground salt mine commenced production 
at Windsor. 
In 1957 a growing public awareness of ecological 
pressures resulting from largo scale diverse industrial 
activity in the Province prompted tl^e formation of the 
Ontario Water Resources Commission. The prime task of the 
Commission was to ameliorate waste discharge problems 



9S 



resulting from active mining operations in Ontario. 
However; at the same time, it was recognized that a total 
solution to the problem of mine waste control could not be 
obtained without control of outstanding problems created by 
a large number of abandoned properties in the Province. 

It took a decade to acquire an undertanding of the 
special mine waste control problems confronting industry 
and government alike and to develop and implement the 
technology required to solve the majority of those 
problems. By 196t., however, a:^ effecKve abatement 
function had been firmly established. As a result, more 
attention could be focussed on the diverse environmental 
problems presented by Ontario's derelict mining lands. 

In the early 1970's the Ontario Water Resources 
Commission was amalgamated with other government groups and 
■evolved into the present-day Ontario Ministry of the 
Environment. During this period of time, several major 
advances were made by the Ministry in areas such as acid 
mine drainage, the toxicity of mine-mill reagents, the 
design and siting of t.iLings disposal sites, and mine-mill 
waste water recycling. Many cpm^rehensi ve reports were 
published and includi_- thr. Tol lowing: 

(a) Guidelines for Knv ironiaontal ConfL-ol in the Ontario 
Mineral Industry 

(b) Mine Waste Control in Ont:ario 



99 



(c) The Use, Characteristics and Toxicity of Mine-Mill 
Reagents in the Province of Ontario 

(d) The Problem of Acid Mine Drainage in the Province of 
Ontario 

(e) On Land or Under Water? The Tailings Disposal Probl 



em 



In 1977, the Ministry of the Environment received 
funding from "The Provincial Lottery" Corporation to 
augment the Ministry's Abandoned Mines Program. This 
funding gave Ontario a running star, on an extensive 
environmental program which should ultimately remove the 
threat of contamination from abandoned mines and restore 
thousands of acres of scarred landscape to their proper 
natural state. "The Provincial Lottory" funding also 
enabled the Ministry to publish a 234-page report entitled: 
"The Chemical Characteristics of Mineral Tailings in the 
PL-ovince of Ontario". This report described, for the first 
time, the extent of the problem of abandoned mining 
operations in Ontario and the specific contaminants that 
must be dealt with. 

At the end of 1978, there were 17,073 acres of tailings 
in the Province that were regarded as still being active 
(that is, associated with currently active mining 
companies) and 7,694 acres that wero' regarded .s abandoned. 
The active areas contained ',^4 1,252,000 tons of mineral 
t.nilings while the abandoned areas contained an additional 



100 



336,100,000 tons. In summary, therefore, at the end of 
1978, in Ontario, 1,077,352,000 tons of tailings were 
contained in areas covering 24,767 acres. These figures 
are not static, however. Active mining operations in the 
Province produce over 100,000 tons of new tailings each day 
and active tailings areas, when filled, are transferred to 
the "abandoned" category. In fact, the total tonnage given 
for tailings on the ground in Ontario at the end of 1978 
has to be increased by 110,000,000 tons to make it current. 
Simply put, the volume of mineral tailings produced in 
Ontario from 1770 to 1978 (208 years) is now being produced 
in less than 10 ye^rs. This rate is accelerating. 

Several hundred tailings disposal areas exist in 
Ontario and these range in si:^c trom less than two acres to 
over 1,000 acres. A common size for these tailings areas 
is from 50 to 300 acres. 

In brief, poorly controlled tailings areas exposed to 
the atmosphere can give rise to environmental problems 
which may include one or more of the Eol lowing: 
1. Leaching of contaminants from the tnilims with 

subsequent impairment nr .lownstream areas. Routinely 

encountered contami lUint,;:; jts.-lritie t^cl^iairable metals, 

acids, cjrscnic an^l ra'^.U'vt:;^^!; -^ipr-f . 



101 



2. Physical deterioration of a tailings area by natural 
processes such as erosion. Existing tailings dams and 
decant structures may be weakened to the point of 
failure. upon failure, large volumes of contaminated 
sediment can be carried to downstream areas. In 
addition, wind can liCt contaminated material from the 
surface of a tailings masr. and transport it long 
distances . 

3. Contamination of local groundwater supplies. 

4. Contamination of local vegetation and animal life by 
processes such as metal uptake rind bio-accumulat ion . 

Given the fact that significant ncreaqes and enormous 
volumes of irdneral tailing:; are available, it is not 
surprising that many attempts have boon made to develop 
large and small scale uses for waste mineral tailings. In 
fact, due to the great amount of energy required to reduce 
solid rock to the sandy oi: silty consistency of tailings, 
the need to conserve energy supplies and the serious 
environmental problems that arc sometimes created by these 
deposits, every effort should bo made to encourage the 
re-use of discarded mineral tailings. In addition, in 
order to help conserve supplies of non-ronewable, naturally 
occurring substances, efforts to win r-sidual mineral 
values from tailings masso:^ f-hould he ^^ncouraged. 



102 



In spite of the above statement, some tailings deposits 
should be regarded as unfit iior re-use or as unfit for a 
particular use due to one or more of a variety of factors. 
These factors may be physical, chomical, and/or radio- 
logical in nature. 

The chemical and piiysical characteristics of any 
specific tailings deposit depend on the geology and 
mineralogy of the deposit being mined, the mining mathod 
being used and on the milling procedures that are (or were 
being) followed in order to liberate the required mineral 
values from the ore. Even within the same mining camp, the 
chemical and physical characteristics of individual 
tailings masses often {although not always) vary widely. 

Over the years, there have been many notable instances 
of contaminated discharges from active and abandoned 
tailings deposits in Ont.ario, Clo,s-^ fjxamination of these 
discharges frequontiy rn^?caled a -.'OmiTlr-x civomic.-il nature 
that was larcviously un:u]?-r'crt(-(i . 

Given all of the arov.j, thr- Ontario Ministry of the 
Environment in the summer of I'VIl , began its concentrated 
drive to deal with the problem of abandoned mining 
operations. ^ 



103 



The program, as developed, is being implemented in four 
discrete stages: 

Stage (1) The documentation oC all inactive and abandoned 
mining operations in the Province in terms of location and 
ownership. Several thousand such properties exist. 
Stage (2) The determination, i n a prel iminary sense, of 
tlio environinental impact ol= ■suocific prcH"^erties and, in a 
preliminary sense, the roccMnmendat ion of remedial measures 
to be taken at these properties. 

Stage (3) The development, as required, of detailed 
environmental impact assessments for chosen specific 
properties and the development, as ro.;iuired, of necessary 
control technologies. 

Stage (4) The actual implementation of control measures at 
chosen specific properties; in other words, the arrangement 
of Provincial participation in t)ie implementation of 
remedial measures where the responsible party cannot be 
idcnti i ied . 

Stage ( 1 ) of the protjram was completed by the end of 
19 7 8 in that the inact i \'c and aha-idmioH minintj operations 
in tiie Proviiice were loc-itod and own(M-:;li i.p icfined when and 
where possible. Since 0'.;rr -i r.h :p oT th -^so pronortios 
clianges hands routinely, thoi_e i r= r-r i-,;-.. uiCficulty in 
keeping files i:urrent.. 



104 



Stage (2) of the program, that is the dGtermmation in 
a preliminary sense, of the environmental impact of 
specific properties is currently noaring completion. This 
stage of the program presented complex difficulties due to 
an almost complete absence of rel table chemical data 
relating specifically to Ontario's tailings masses and 
known tailings mas so sin ge no r a I . Th o Ministry, there fore , 
had to generate its own drita brise and thTs conld only be 
accomplished by carefully sampling all accessible tailings 
areas in the Province and then subjecting all acquired 
samples to detai lr-(' chemical i nvest igat i.-'/ns . Tn fact, over 
4,000 individual l^ilings an-ilyKos, covering 32 different 
chemical parametor^^ were am.as-.c.i during the proMram and 
formed the basis o\ the report nlready mentioned entitled 
"The Chemical Characteristics of Mineral Tailings in the 
Province of Ontario". This report serves to indicate areas 
where potential environmental problems exist. Tn the 
summer of 1980, the sampling program was extended to cover 
areas previously not sampled and to confirm prior results 
where potential environmental problems wcrf indicated. 
These new samples, already acquired will be ut^ed to 
determine the rad Lological characteri sties of al I Ont-ario 
tai 1 ing;^ masaer., .vtul in f.^rct, h.-ive al ready boon r-ubjected 
tn a t^r'.-J i iiii nary a<i.j.i;!i.i;a r'l.t- ' n^' i ;vm ■'■-■.cr.tii.cni ng . Prc^'o-'^'^d 
te.sti 11'! wi I ' «'onti Lin .ind ' -.niip li-mnn t pi ev i ouli r-Jr-sultr.' and 
expand the original dal.i ba,;o ih bh^^t many addi tional 
chemical parameters wil ] also iv d.n'tf.-rmtned . 



105 



At this time, the concept of revogotation is a popular 
and useful solution to many of the problems associated with 
derelict tailings areas. Por this reason, it was con- 
sidered advantageous to collorl- samples of any veqetation 
that was found to exist in tiarmony with the mineral 
tailings already sampled. As a result, in 197fi, different 
varieties of vegetation wei/e sampled at 35 inactive and 
abandoned mineral tailings areas in Ontario, and analysed 
for 23 different parameters. It was also necessary to 
collect samples of similar species of vegetation growing in 
areas removed from the sample sites for use as controls. 
Similar sampling was completed in the summer of 1980 and a 
report detailing findings is being undertaken. 

With stages (1) and (2) of the project virtually 
completed, the abandoned mines program is now being 
accelerated in an attempt to achieve an early resolution of 
problems of immediate concern. 

The first priority of thxr projoof. involves the re- 
clamation of tho-o abandrned mines or t."i lings areas that 
pose immediate or potential ha7ard;-, l.o human health or to 
established communities . 

In a strictly theoreliical .sens(>/ there are tew, if any, 
substances in the universe that can truly be described as 
"inert". Sooner or later, r^ven thr most resistant 



106 



substances are conquered by the £orccs of their 
environment. Taking this point of view, all the materials 
found in a tailings area are eventually free to escape the 
area. The most nr^seniial in':M;.;.>lirint in t!iii-j typo of 
approach ir, the o] -ment of tiT.n. Ir, most crises, the time 
required foi the ni ssolut i ntrr- or roactior.r. tvi (jq to 
completion appcOKi-^iatc-s t'niil ul hnndref'is or i'houriaads of 
human life spans. On a day-to-day, or short term basis, 
this approach to environmental |jroblems generated by 
existing deposits of mineral tailings is not practical 
except perhaps in a few instances such as those involving 
specific long-lived radioisotopes. Since the Abandoned 
Mines Prograin of the Ministry of the Environment Is 
intended to be a practical t^rogram, the reclamation 
concepts involved are intended to be efTectivo over time 
periods of perhaps a century or more as opposed to 
thousands or hundreds of thousand? of years . Wh ile it is 
recognized thai- over .periods of luindrods or liundrcds of 
thousand's of yeni::i^, most C(imponen:fs of a tailings area 
including tl^e mineral r.il i.-.ahpf, will undergo ;-;o;ntj degree of 
chemical or fliysicU chnnnv..^ it iff also recogni:'.ed that the 
mO'S t c^;rem-.?:iti components oi i-iio --^nrth's crust will also 
uniergo similar ciianges gi\-.-'n the same physical and 
chemical condi tio^^■; . Thc: iuilk ol" the vast majority of 
tailings masses located in niitra- i o '^) hardrock mining 
cUstrict consists o[ a variety of relatively stable 
silicatfir, ant] oxides. i'rn^n ,in environmental standpoint, 



10? 



therefore, we restrict our interest to those mobile 
elements or substances that commonly occur in tailings 
areas in above average or abnormal concentrations. with 
this in mind, the high level of sulphur and arsenic 
routinely encountered in Ontario taiUngs areas should be 
noted. The stresses that can be placed on the environment 
by these two elements and their associated compounds are 
well documented. The low level of calcium noted in these 
tailings areas is also of .ntero.t .ince calcium compounds 
are, in large part, responsible for the acid neutralizing 
capacity that any specific tailings mass might have. 

As a result, on a Province-wide basis, the t.vo most 
important environmental problems that are likely to be 
encountered at Ontario tailings disposal sites are the 

control of : 

1) sulphur and suJohur compoun-ls , and 
1) arsenic and arsenic compounds 

The unstable sulphur compounds cor^monly found in 
Ontario tailings niasses have the ahilitv to spontaneously 
decompose to liberate larno ..ount., ., (sulphuric) acid and 
associated metals. The local environmental offects of 
these discharges are rouMnely deva.tln., and, coupled with 
the problem of. acid rain, can ,, i .e >:'i,s.^ to reoional acid 
problems. 



108 



Arsenic, long knov;n for itr. toxicity to humans, also 
occurs commonly in a variety oi Lorms in Ontario tailings 
areas. Arsenic is a mobile substance that responds only 
grudgingly to accepted forms of waste treatment. 

While sulphur and arsenic present us with the most 
pressing waste control problems nt abandoned Ontario mining 
sites, we are frequently faced with other problems nuch as 

the transportation ity wind or water of a variety of sub- 
stances including asbestos; rndionuclides such ns radium 
and thorium; mercury, a ho torotjeneity of metals and non- 
metals and a perplexing a:.-rav f^f residu3l mino/mili 
r e a g t : 1 1 1 55 . 

In the past, tai lings ma5;ses in the Trovince !iave been 
cliaraeter ized as : 

1 ) s imple sterile soils, an(5 

2) as rich deposits of almost every metal. 

In reality, neither of the above is strictly true. 

Compared co the chemistry of th«; earth's cryst, Ontario 

tailings areas are routinoTy.:. 

depleted in ;^ubstanc(^s su'-h -a^': sodium 

magnosiuMi 
i^'' nor inc 
"vlum i.nnm 
p!fO:-,t''-.orns 
■i 'ili.vri.ne 

■i' ' lA: f i;m 
f. i i Miium 
man(n."'.nosf? 
■r-f.r.i>nt i um 



109 



barium 
molybdenum 

and enriched in such substances as: nitrogen 

vanadium 
chromium 
iron 

cobalt 
nickel 

copper 

zinc 

arsenic 

selenium 

cadmium 

tin 

antimony 

bo ro n 

mercury 

lead 

bismuth 

sul phur 

There are, of course, individual exceptions to all cases 

above. Th.^ causes, or probable caLi:-:cs ot: the- enrichments 

or depletions noted can bc: ex|)lainod with relative ease in 

most cases. Explanations liv-zo] vo concepts of mineralogy- 

yeology and intimate knowledge ot mine mill process 

technology . 



In Ontario, it is expected that: 

1) the reclamation of derelict mining lands will largely 
be acliieved by revege ta t ion . Other methods of 
stabilization of these areas will have to be used when 
and where revegetation is not foo-^ihlc. 

2) tlie ov/ner of the land involvf.'i, -in. I not the public, 
wil 1 pay for the reel ar i Li ,-,ii nf (.he land, aiid 

3) every attempt v;ili b-^ I'.udo l,o f^chirvo a "walk -away" 
situat ion upon the coi.t;;! r^i i .v; rH r^c lamat ion at ativ 



110 



particular property. A "walk-away" situation is 
exactly what it sounds like: no maintenance and no 
monitoring. 

The reclamation by revogetation of Ontario's abandoned 
mining properties presents problems that are somewhat 

obvious but are frequently overlooked by those demanding 
immediate action in any particular area. For instance: 
(a) Many abandoned areas are quite renmte. As such, accesi; 

to the property can pr.:n.enb great difficult i.es, as can 
the co:T;plete lack of: ;waM-^ble ntilitins sur-h as 
electrical power. Tn .oxtrc ^i^ ceases, seeding of 
derelict mining lands, .^y ha-^t^ u^ bo acco.ppl i shed Erom 
aircraft. 

(b) Reclamation by revogo l-.i i inn :- nu^it mining areas in 
Ontario can routinely on]y bo carried out during a few 
weeks in the spring and pcri^aps a Tew weeks in the fall 
of the year, 

(c) It may take well over s years to produce a successful 
self-sustaining vegetative cover. 

(d) The revegetation of derollcf nining lands is a young 
science and qapa in technology do exist, I'his is 
particularly t-^ .where ..cid ^.ining lands are involved. 

Ce) It is (--.urrcntly -st ino r , 4 H-i ,:ostr for fc:He 

:.-erl.,:iaa.l:Loti o) a)! -^l n,fl.dx.r[j'4 :ul:U.ng 1 ^nds i., i.hc 
province now c^ccr I l;r. .■ ^ .; M , n .:'n.ar.., Can.Adian. 



Ill 



Up to the present time, j ur isd ict ion in Ontario for the 
reclamation of mining properties has not rested with the 
Ministry of the Environment. Instead, all references to 
reclamation wore found in the Ontario Mining Act. As a 
result, the Waste Management Branch of the Ontario Ministry 
of the Environment recently moved tt^ transfer this juris- 
diction directly to the Ministry of the Environment. This 
task has been essentially completed. 

As a result, an al 1 -encompassing and specific program 
of reclamation should be possiblf; in the Province of 
Ontario beginning oarly in 19S1. This program, is expected 
to include the following: 

(a) All new, active, idle, and aban'loned mining operations 
in the Province of Ontario will report to the Ministry 
of the Environment within a given period of time 
concerning their specific abandonment or reclamation 
programs. These programs should be to the satisfaction 
of the Ministry of the r:nvironment and should be 
completed within an agreed to time frame, 
{b ) In essence, it is expected that ■ ir one rty owners will 
plant and maintain vegetation o*; otherwise stabilize 
all despoiled areas on theii- iiroperfy including mine 
tailings areas, was!. '-fH'.l; disjins.'l sites, and any 
sites containing relate...! debris: 



112 



(c) A bonding mechanism is proposed to be used when 

required to ensure that roclamation procedures are 
carried out as specified. 

In summary, tht; Abandoned Mines Program of the Ontario 
Ministry o£ the K/ivironmont tias evolved into a precise 
mixture of inver^t ig^iti ve njr.o.ircb and lofjir.lat i on . With 
the rapidly rising cost.^ of roclamal: ion, ^ successful 
conclusion to the project is deemed hot. It timely and 
necessary. Durinci 1981, the .actual ol-ocoss to transform 
thousands of acres of steri Ic vjnste land into 
indistinguishable parts of the natural countryside should 
begin . 



113 



METHODOLOGY FOR DEVELOPING A 
QUANTITY AND LOCATION INVENTORY 
OF HAZARDOUS COMPOUNDS IN ONTARIO 



P. J, Denison and K. R. Ashwood 
Acres Consulting Services Limited 
Niagara Falls, Ontario 



INTRODUCTION 

A 2-year contract was awarded in 1978 by the Air Resources 
Branch, Ontario Ministry of the Environment to inventory 17 
specified chlorinated and aromatic hydrocarbons in Ontario. 
The chemical compounds of concern in this study were 



Chlorinated Hydrocarbons 
Carbon tetrachloride 
Chloroform 
Chloroprene 
1 , 2-Dichloroethylene 
Ethylene dichloride 
Methyl chloride 
Methylene chloride 
Tetrachloroethylene 
1,1, 1-Trichloroe thane 
Trichloroethylene 
Vinyl idene chloride 



114 



Aromatic Hydrocarbons 

Benzene 

Ethylbenzene 

Naphthalene 

Styrene 

Toluene 

Xylenes 

The base year for this study was 1976 since this was the 
most recent year that published statistics were available 
when the project commenced. 



DATA REQUIREMENTS 

The terms of reference for this study required that it be 
completed in two phases - 

Phase A: Quantity and Location Inventory 
Phase B: Emission/Discharge Inventory. 

The requested information for Phase A consisted of the 
following for each selected chemical. 

1 . Company name and address 

2. Plant address and industrial activity 

3. Quantity in storage 

4. Quantity produced/used 



im 



5. Quantity imported/exported 

(a) from/to other provinces 

(b) frcMn/to other countries 

6. Method of shipment (road/rail/air/sea). 



For Phase B, the emission/discharge inventory, the study 
objectives were to obtain the following data 

1. Amount released (rate) 

2 . Frequency (continuous/intermittent/seasonal) 

3. Source of release 

4. Control devices 

5 . For water - receiving water system 

6. For soil - receiving disposal site, 



A description of process operations was also required to 
enable comparisons to be made with published emission factors 
However, it is recognized that each plant has its own unique 
conditions and actual data from Ontario plants were used 
wherever available. Releases from storage and handling 
facilities were also considered in this phase of the study. 



116 



DATA SOURCES 

The first step in preparing this inventory was to document 
all potential end uses for the chemicals. This was accomp- 
lished with assistance from Corpus Information Services Ltd 
(chemical market consultants) , and by referencing a number 
of organic chemistry handbooks and journal articles. Next, 
potential primary and secondary manufacturers, distributors 
and end users for the uses identified were obtained from a 
number of trade directories and through acquiring membership 
lists from these associations whose members are involved 
with the chemicals of concern. 

Data on imports and exports were obtained from Statistics 
Canada and the U.S. Department of Commerce. For emissions 
and discharges, limited information was obtained from the 
U.S. Environmental Protection Agency , Environment Canada , 
A. D. Little Inc. , GCA Corporation and Monsanto Research 
Corporation. 



DATA GAPS 

A review of the published data confirmed that much of the 
information was not available without making direct contact 
with the companies concerned. Specifically, bhe data gaps 
were as follows : 



117 
Phase A - Quantity/Location Inventory 

1. Quantitative data on production, usage, storage, 
imports/exports 

2. Method of shipment 

Phase B - Emission/Discharge Inventory 

1. Quantitative data on emissions/discharges 

2. Site-specific data on control devices, receiving water 
systems, waste disposal sites. 



QUESTIONNAIRE DESIGN 

Separate questionnaires were designed for distribution to 
Ontario manufacturers and distributors, Quebec manufacturers 
shipping to Ontario customers, and potential Ontario users 
of the specified chemicals. 

Information requested for each chemical included 1976 
production, consumption (as a chemical intermediate and as 
a component in a mixture or blend) , annual inventory levels, 
purchases from outside Ontario, and distribution within and 
outside Ontario. For emissions and discharges, information 
was requested on losses to the air, water and land including 
evaporative losses from storage and transfer facilities. 
Details on control devices and efficiencies, emission 
frequencies and a range of average daily emissions were also 
requested. 



118 



SUMMARY OF SUCCESS 

Approximately 60 percent responded to the questionnaire 
survey. However, these responses covered 90 percent of the 
volumes produced or imported and subsequently used in 
Ontario, 

It was found that 3 of the 17 hydrocarbons (chloroprene , 
1, 2-dichloroethylene and vinylidene chloride) were not in 
commerical use in Ontario in 1976. 

A review of transport modes indicated that the specified 

chlorinated hydrocarbons are transported primarily by 

road, with rail being the next most common method of shipment. 

The aromatic hydrocarbons studied are being transported 

primarily by pipeline , with rail and road being of lesser 

significance. 

While production and consumption information from primary and 
secondary manufacturers could be geographically plotted accu- 
rately, a difficulty arose in plotting widespread end use for 
some of the specified hydrocarbons. For example , approximately 
80 percent of the tetrachlor ©ethylene produced and imported 
into Ontario was consumed by the dry cleaning industry in 
1976. To calculate industry end usage for this chemical by 
city in Ontario, we determined there were 1 , 154 dry cleaning 
plants in the province from Statistics Canada and telephone 
directories. From a spot survey of 9 dry cleaners in Toronto, 
St . Catharines and Niagara Falls , an annual average of 5.6 
tonnes was used. Assuming all tetrachloroethylene used by 



119 



the dry cleaning industry is eventually lost to the atmosphere, 
losses were plotted by multiplying 5,6 tonnes time the number 
of dry cleaning plants in each city. 

END USE PATTERNS 

Those specified chemicals with widespread usage deserve 
particular attention since their emissions and discharges 
are believed to constitute 100 percent of the amounts used. 



Chemical 



Examples of Widespread 
Usage in Ontario 



Methylene chloride 



paint stripper, paints, 
cleaning solvent 



Tetrachloroethylene dry cleaning solvent, 

metal degreasing, textile cleaning 

1, 1, 1-Trichloroethane metal cleaning, degreasing 



Trichloroethylene 



metal cleaning, degreasing 



Toluene* 
Xylenes* 



solvent in paints, resins, adhesives, 
rubber process ing , metal cleaning , 
printing ink reduction, gasoline additive* 



*Toluene and xylenes used as gasoline additives were quantified 
only as far as total amounts used in Ontario; geographical 
distribution in gasolines was not considered. 



120 



Based on the known amounts consumed in these widespread 
applications, a loss factor per capita (or per company, 
depending on the type of usage) was calculated to enable 
geographical plotting of the data. 

The Ontario emission/discharge inventory covered specified 
chemical losses to the air, water and land during manufacture, 
its use as a chemical intermediate, storage and transfer, 
repackaging for distribution and end use. Storage and 
transfer losses of benzene, toluene and xylenes in gasolines 
were included at refinery locations; other losses of these 
aromatics at local filling stations or from vehicle exhausts 
were not included. 

Bearing the above points in mind, 2 maps have been prepared 
showing 1976 losses of the specified chemicals in Ontario 
(Figures 1 and 2) , While these maps show only totals for 
all 14 specified chemicals, detailed maps for each chemical, 
showing all affected Ontario locations were submitted to 
the Air Resources Branch, Ministry of the Environment. 

In conclusion, based on the 1976 results obtained, there is 
no indication that emissions and discharges of the specified 
chemicals approach current preliminary estimates of hazard 
levels outlined in MOE guidelines and standards. However, 
due to the limited amount of ambient air quality data 
available, it has been recommended that additional quanti- 
tative information be collected to enable a more accurate 
assessment of the situation. This may become critical in 



121 



view of the controversy centered around many of these 
chemicals suspected of being human carcinogens. Also, we 
are not yet fully cognizant of the effects of chemical 
interactions which can be independent, additive, synergistic 
or antagonistic {i.e. the effect of one chemical reduces 
the effect of another chemical) . Until more scientific 
evidence is available, it is necessary to take a cautious 
approach by compiling inventories of suspect chemicals. In 
this way, if and when action is required, the Ministry has 
the capability to proceed without delay. 




^u^oti 



GUELPH 

waterloo q 
stratfordO 



— T-KO^^STfCATHARINES 
O O NIAGARA FALLS 

WOODSTOCK O BRANTFORD OVORT ERIE 







SARNIA® 



LONDON 




LEGEND 


O 


500-1000 TONNES 


• 


tOOO- 2000 TONNES 


• 


2000-5000 TONNES 


® 


5000-10000 TONNES 


▲ 


> 10000 TONNES 



FIGURE I -SAMPLE DISTRIBUTION OF EMISSIONS a DISCHARGES 
FOR 14 SPECIFIED CHLORINATED a AROMATIC 
HYDROCARBONS IN SOUTHWESTERN ONTARIO 



N3 

W 



OTTAWA RIVER 



barrieO 



RICHMOND HrL 



BRAMPTON 

WILTON C 
OAKVILLE: 



PETERBOROUOH 



MILTON 0jf»S„,,;^ 





LEGEND 


o 


500 - 1000 TONNES 


• 


1000 - 2000 TONNES 


• 


2000 — 5000 TONNES 


® 


5000 - (0000 TONNES 


A 


> 10000 TONNES 



FIGURE 2-SAMPLE DISTRIBUTION OF EMISSIONS a DISCHARGES 
FOR 14 SPECIFIED CHLORINATED a AROMATIC 
HYDROCARBONS IN SOUTHEASTERN ONTARIO 






12^ 



ONTARIO'S SEVEN POINT PROGRAM FOR LIQUID INDUSTRIAL 

WASTE DISPOSAL Ministry of the Enviromni^ 



Liquid and Special Industrial 
Waste Management Program 



1,. FACILITIES 

- Work with private sector 

- Long-term waste management plan 

- Acquisition of sites 

2:. INTERIM MEASURES 

- Guidelines 

- Treatment and Disposal 

- Landfill Prohibition 

- monitorint^ and control 

- Waste Storage 

- PCB 

- Other Wastes 
3. WAY-BILL MONITORING 

- EDP System 

^. WASTE CLASSIFICATION 

5. REGULATIONS 

- Landfill Prohibition 

- Treatment and Disposal 

- Rrr, I strati on of 1/astes 

6. PERPETUAL CARE 

- Study 

- Regulations 

7. TRANSBOUNDARY MOVEMENi OF WASTES 



125 



FACILITIES FOR LIQUID INDUSTRIAL WASTE TREATMENT AND DISPOSAL 



a) government 



MacLAREN STUDY 

Long-term wastc management plan 

Five years to develop and implementC?) 



b) private sector 



Region of Durham Proposal to Convert The Ajax 
STP into Physical/Chemical Treatment Facility 
Environmental hearing under The 
Environmental Protection Act commenced 
December 17. 1979. Due to be completed 
June 20. 19P0, 



c) PCBs 



1.. MacLaren Study to incorporate need for 
PCB destruction facilities 

2. St. Lawrence Cement kiln 

- Test Burn 

- City of FIississauga By-law 



126 



INTERIM MEASURES 

1, LIQUID INDUSTRIAL WASTES 

a) Improved monitoring and controls on 22 
landfill sites currently accepting liquids 

b) Limited-term (five years) solidification 
proposals 

- Browning-Ferris Industries Limited 
AT Ridge Landfill site in Township 
OF Harwich 

- Walker Rrotijers Quarries Limited at 

QUARRY SITE IN St. CaTHARINES AREA ' 

- Proposals subject to The Environmental 
Assessment Act 

- Ministry of the Environment co-proponent 

- Documents filed with Minister on May 9. 1980 

- Hearing in late Fall? 



127 



INTERIM MEASURES 
2. PCBs 

a) M. M. Dillon Study on Interim Storage of PCBs 

- Review of Crown Lands (and others) in 
Province 

- Three preferred sites 

Ontario Hydro Transformer Station in 

fllDDLEPORT 

Cayuga Properties 
Ridge Landfill (BFI) 

- Ministry elected to proceed with MIDDLEPORT 

- Government owned land; 

- Close ro ccntroid of waste PCB 
generation; 

- Reason/adll road access; 

- Not closf to urban area 

- Subject to Environmental Assessment Act 

- Consultant presently preparing assessment 
documents (6 months) 

b) Regulation on Movement of PCBs 

(To BE dealt with later) 



' 11 



WAY-BILL MONITORING PROGRAM 

New way-bill introduced in January, 1979, 

proving to be a definite improvement 

Study completed on optimal approach to 
handling way-bills and processing data 

- An 'intelligent terminal' located in Waste 
Management Branch will be used to input data 

AND produce minor REPORTS. ThIS WILL BE 
supported by the GOVERNMENT MAIN COMPUTER 

for the production of major reports and 
statistics. 

- New system to be in place this year subject 

TO EQUIPMENT DELIVlRY 



128 



129 




Transfers of Liquid 



Ministry , ransiers 01 Liqiiici r* ooon o 

Environment Industrial Waste 

Ontario Ontario Rctjulntion 9:?G/7fi 

imporUint: Zi'ff Insrruaions on 'Ici'rrsV 
oUURCE (Complete Section A Onlv/. Plpasc Pnn'i 



— 1 1 \ 1 I i_i_..: i.. 



ConipdnY Nama 



-J._-i, 



Wsita Source Locauon 



t-_..:l 1_... i. 1 ...L ^_ ,1... ;i J , .J 



Cily/Tov/ri 



Wunfl Dr^icriiHion; Chwcl. OnE, 



201 riOUv V.„ti-i 
207 DWjiii' Oils 
20.T l]OrB.ini< K(>K'm:u -f*^ i.] 'TjtkiilM 



UH [ 1 P (iTicjif!. P,ii:.I. f'rinung 



101 DAckU 
lOV nAJk.ih* 

WE ri,-^ r -•y'* n PfiKtmaciiinicBi 

105 GLh.o...iroM„,....,W...,n. :>0r, l,A,n,n,.s ^Co,,nm,„ 

208 Gfhunoli 40.' [ :i [nor i Slinlflo* 

209 Grca-s 



190 QOtl.e. _„ 



?00 nOihnr 

O'Oanic 



— V- --'--■■ ' —1-.. .J..,. I I 

Day Momh Vei.i .!;'t)i-..,Hi.,. nl A,iHiom.'.'m P*'.iofi 



■ Sp^ci f V I 



7 imu 
Holosicd 



RECEIVER (Complrrr Sectio 



B 



^ : —^ L — 1 1 I. 



^Section B 0,-,!v Plo.lSr' Pt :nll 



C'.jniinny fJinie 



fwOr r.i; riHH.CKi of A;!pro/al No 



C.iy/Tovun 



Tl Bn(f or 

To 



.firt'if i;}'Jur;L,..- Landfill 



T.n.f 



l.VH M-.inlh Yo,vr I r.fjr.,THir.> cr At.lh 

__1 L_ 



I ■ . Hvtr 'Stii'ft McthodI 



("nrsr.-n 






UAhRIER (Comtil.-K Sfcl.cn C Oiiiy. l-lc.isi' f'i mr) 



<;in.M'i"'v N.i'Tie 



'■^■M";N NLrnil, 






I ■■'-.'.■:■ r-l'imt liy.n-if N,.ni|,'-i 

.'lI'IM.II.IOr t I [iriv.f ■«-.'^' -- - ■ ^^ -L ^ 



(.■Of. 1270 17 7<i; 



I VI 



INr^ :";"N'"S CO 



130 

QUANTITIES OF LIQUID INDUSTRIAL WASTES GENERATED IN ONTARIO 
(Summary Report) January to December, 1979 

WASTE CLASSIFICATION VOLUME (GALLONS) 

101 Acids ^,060,100 

102 Alkalis L7%.000 

103 Metal Finishing Wastes 2.8^7,^00 
10^ Cyanides -41.700 

105 Chemical Fertilizer Wastes 6^L100 

106 Phosphates 252.000 
190 Other (Inorganic) 7,076.600 

201 Oily Water 1^1,542,000 

202 Waste Oils 2,W,800 

203 Organic Solvents 2,839,200 
294 Chlorinated Solvents 95.800 

205 Plastic Resins 1,094,900 

206 Amines 279,200 

207 Glycols il2h500 

208 Phenols 503,700 

209 PCB's 14,500 
290 Other (Organic) 3,99L000 

301 Pigments, Paint, Printing and 3,184,300 

Adhesives 

302 Pesticides 215,000 

303 Detergents, Cleaners and Soaps 402,000 

304 Pharmaceutical and Cosmetics 22,000 

401 Plant and Animal Wastes 2,819,290 

402 Inert Sludges ^ 11,094,900 
Unspecified ' 874,000 

GRAND TOTAL 61,547,100 



131 



LIQUID INDUSTRIAL WASTES 



DISPOSAL HFTIIODS 



.1979 



VOLUME 
'•iiLLiONS OF Gallons) 



INCINERATION ig.O 



LANDFILL 36,0 



EXPORT 5,0 



MISCELLANEOUS 1,5 



HAL 61.5 



132 



REGULATIONS AND GUIDELINES 

1. REGULATIONS 

a) Movement of Equipment Containing PCBs 

- Draft completed and approved. Waiting for 
administrative guidelines. 

b) Registration of Wastes 

- Study completed of approach in other 
jurisdictions throughout world 

- Regulations expected to be drafted by end 
of year 

c) Prohibition on Landfilling of liquid wastes 

- Regulation in abeyance pending 
availability of alternative treatment and 

disposal FACILITIES 

2., GUIDELINES 

a) Pollution Prevention and Waste Management 
Guidelines for PCBs. November. 1978. to be 
revised. 

b) Waste Classification Guidelines to be revised 
consistent with registration of waste 
regulation 

c) Treatment and Disposal of Liquid Industrial 
Waste Guideline to be updated or converted into 
Regulation 

d) Waste Oil Guideline to be revised pending 
policv on road oiling 



133 

PERPETUAL CARE PROGRAM 

Task Force established early in 1979 

- Terms of Reference to ensure source of funding 
for short-term and long-term (after closure) 

contingencies at landfill SITES 

Concluded that measures required in: 

a) Operational sector during operation and 
closure and for subsequent monitoring and 
maintenance 

b) Liability insurance - Off-site protection 
for third parties 

c) Care in perpetuity - to provide long-term 
maintenance and protection and for 
contingencies not covered by other measures. 

- Work was delayed pending report from consultant 
on availability of insurance. 
Details now to be resolved: 

a) How can owners of sites be required to 
secure the necessary funding? 

b) What is reasonable level of insurance? 

c) What are reasonable surcharges for the 
establishment of perpetual care fund? 

- Report expected to be finalized by end of year. 



134 



RANSBOUNDARY f'OVEN^;NT OF WASTL'S 

Ministry oh tut. Fnyironmi^nt and Environment 
Canada working on di-velopment of a Manifest 

SYSTEM FOR I NTERNAT IONAl/ HJTER-PROVI NCI AL 
MOVEMENT UP WASTES 

MOt RlM/^INS SIJPPOFIFIVF OF 'OPEN BORDER' POLICY 
0W WA;-TF nivSPOSM 

fflE Ai-JD riU'HTGA^ ^F-EVALUATING METHODOLOGY FOR 
AUTH*^iviZUm V/AnTF I'vAfiSFFRS, 

CiJRiwZi-iTL'i ?'^0'*/r:^THl ^:>r wastes I?; 

O.KrAKio -lO US- :;fln.00n gals/montk, 

U.S,^ iT QnihHU' ■■ 80-90.000 gals/month 

r.L.H i^vK : li ..WASU. r^ "A^ ri: r'.(.,o ro U.S. secure 
LAMiP;iis f0H niJ^rasAi, 'lY 0Nr: contractor in 



135 



The Honourable Harry C Parrott, D-D-S 
Minister of the Environment 



Statement to the Legislature 

Re: Ontario Waste IIanagement Corp 
(Statement of Policy) 



Queen's Park, Toronto 
November 25. 1980 



136 



Mr- Speaker: 

as i indicated in the house two weeks ago, i have 

RECEIVED THE MacLaREN RePORT WHICH RECOMMENDS OPTIONS ON 
PERMANENT LIQUID WASTE TREATMENT FACILITIES- I HAVE HAD AN 
OPPORTUNITY TO THOROUGHLY EXAMINE THE RECOMMENDATIONS AND 1 
WOULD LIKE TO TABLE IT AT THIS TIME- ThE APPENDICES TO THIS 
REPORT WILL BE TABLED AS SOON AS THEY ARE PRINTED- 

As THE Members will remember, I referred the issue of 

LIQUID industrial WASTE TO THE STANDING COMMITTEE ON 

Resources Development in November 1978- As a basis for 

DISCUSSION, 1 PUT forward A SEVRN-POINT PROGRAM WHICH 
represented OUR PLAN OF ATTACK ON THE LIQUID WASTE PROBLEM- 

AfTER AN INTENSIVE REVIEW OF OUR PROPOSALS AND THE 
PROBLEM IT WOULD ADDRESS, THE COMMITTEE SUBMITTED ITS REPORT. 
At THIS TIME, I WOULD LIKE TO REMIND THE MEMBERS ONCE AGAIN 
HOW CLOSELY WE HAVE TAKEN THEIR ADVICE IN IMPLEMENTING OUR 

SEVEN-POINT program- 



There WERE 47 DIFFERENT RECOMMENDATIONS AND SUGGESTIONS 
IN THAT REPORT. A TOTAL OF 58 HAVE EITHER BEEN COMPLETELY 
IMPLEMENTED OR ARE IN THE PLANNING STAGES- ThE REST ARE 
UNDER ACTIVE CONSIDERATION- 



137 



Obviously, the Committee's report was of great 
assistance to us • 

There were five specific options proposed for 
establishing facilities- In the initial stage of our plan 

FOR short term FACILITIES, WE ACCEPTED THEIR THIRD OPTION "- 
joint PUBLIC-PRIVATE OWNERSHIP OF SITES AND FACILITIES- We 
ACCEPTED THE CoMMITTEE's VIEW THAT WE ASSIST COMPANIES TO 
ESTABLISH NEW TECHNOLOGY- 

We HAVE ACCEPTED THEIR VIEWS AND YET IT IS WITH CONCERN 
AND REGRET THAT I FIND DELIBERATE ATTEMPTS TO HALT 
IMPLEMENTATION OF THOSE OPTIONS* 

I NEED NOT OUTLINE THE LITANY OF EVENTS WHICH HAVE 
FRUSTRATED OUR EFFORTS TO PROCEED WITH RATIONAL HEARINGS- 
CERTAIN ACTIONS HAVE ONLY INTENSIFIED THE PUBLIc's FOCUS ON 
THE "not in my backyard" SYNDROME- LoST IN THAT APPROACH IS 
THE VERY CRUCIAL ARGUMENT THAT THE TREATMENT PROPOSED IS THE 
ONLY WAY TO GUARANTEE THE SAFETY THEY SO EARNESTLY DESIRE- 



Mr- Speaker, it is obvious the amazingly consistent 
response we have received in every location, and experience 
throughout North America demonstrates/ that we are 
encountering a kind of social phenomena- 



138 



My one goal is to stop the landfilling of untreated liquid 
WASTE- That is not only a strong commitment from me, but of 
THIS Government. 

But quite frankly, the controversy surrounding each 
proposal has meant that it has taken too long to implement what 
Tm sure everyone agrees is a legitimate objective. However, 
that interval has been used productively. 

There has been time for the completion of the MacLaren 

Report. And it clearly indicates the pressing need for an 

immediate solution. 

»■ 

Two WEEKS AGO, 1 ANNOUNCED A FREEZE ON MINISTRY ACTIVITIES 
AND PARTICIPATION IN OUR SHORT TERM PROPOSALS- I WANTED TIME 
TO ASSESS OUR OTHER OPTIONS AND TO WEIGH MacLaREn's 
RECOMMENDATIONS. 1n REACHING TODAY's DECISION I RELIED HEAVILY 
ON THE STANDING COMMITTEE'S OPTION OF GOVERNMENT OWNERSHIP AND 
CONTROL AS WELL AS THE MacLaREN RePORT. 



In their first report, MacLaren outlined basic criteria 

FOR assessment OF SITES- It WAS APPARENT THERE WOliLD BE 
EXTREME DIFFICULTY IN OBTAINING ONE SITE TO MEET ALL CRITERIA- 



139 



One MacLaren engineer said: "llNnsiR the criteria agreed 

ON, WE eliminated ALL AREAS IN SOUTHERN ONTARIO WITHIN FIVE 
MILES OF ANY CITY, TOWN OR VILLAGF-- PROVINCIAL AND FEDERAL 

PARK, ALL Indian Reservations, conservation authority land^ 

FLOOD LAND, ECOLOGICALLY SENSITIVE LAND AND ClASS 1 OR ClASS 
2 AGRICULTURAL LAND- WhEN WE GOT THROUGH, THERE WASN't MUCH 

OF THE Province left!" 

In early June 1 requested MacLaren assess two additional 

SITES -' crown land IN SoUTH CaYUGA AREA AND LAND AT CaMP 

Borden, previously suggested by the Federal Department of the 
Environment- 

Besides a lack of suitable sites, it was clear that the 

PUBLIC, AS well as MEMBERS OF THE HouSE, FEEL THAT ONLY 
government CONTROL AND OWNERSHIP WILL GUARANTEE THE SAFETY OF 

THOSE facilities- 



Today's REPORT recommends TllH PROVINCE ACQUIRE ONE OR 
MORE SITES ON WHICH IT V.'OiiLD HE POSSIBLE TO CONSTRUCT WASTE 
MANAGEMENT FACILITIES- It CONCLUDES THAT LAND IN SoUTH 

Cayuga and five other areas has potential for such a site -- 
Huron County, Lambton County^ Rruce County and two locations 
IN SiMcoE County- 



140 



The two sites preferred by MacLaren are the one in Huron 

AND THE ONE IN THE SoUTH CaYUGA AREA- BOTH ARE CONSIDERED 
"viable LOCATIONS FOR THE PROPOSED FACILITIES SUBJECT TO 
THEIR GEOLOGICAL SUITABILITY BEING CONFIRMED BY FIELD 
STUDIES'" 

MacLaREN STATES CaYUGA OFFERS AN ADDITIONAL ADVANTAGE 
BECAUSE IT IS CLOSE TO WASTE GENERATORS- I BELIEVE THE FACT 
THAT THE GOVERNMENT ALREADY OWNS MUCH OF THE LAND IS ANOTHER 

MAJOR PLUS. This allows adequate government control of the 

SITE; A BUFFER ZONE CAN EASILY BE ACHIEVED; AND THERE WILL BE 
MINIMAL DISRUPTION IN TERMS OF EXISTING LAND USE AND TO ANY 
RESIDENTS. ThE ASSEMBLY OF PRIVATELY OWNED LAND 'l N THE OTHER 
AREAS WOULD RESULT IN MASSIVE EXPROPRIATION AND CONSIDERABLE 

cost to obtain the needed properties. 

Before a decision could be made, we carried out soil 
TESTS IN Cayuga. The engineering firm of Morrison Beatty 
Limited was retained- Their report states "the site appears 
to bf ideally suited" for what wl proposl- 

Based on these factors, I have decided that land in the 
South Cayuga area will becomf Tfir Province's permanent liquid 

industrial waste TREATMENT FACILITY- 1t WILL HAVE THE BEST 

available technology and operatl unde'r the highest 
standards- 



141 



One important aspect of fml" government ownership means 
we can and do fully accept the responsibility as a government 
for the operation of such a site* 

The site will be run by a newly formed corporation with 
A board of directors of two representatives from the general 

PUBLIC, two members OF THE LOCAL COMMUNITY, TWO TECHNICAL 
experts and A CHAIRMAN APPOINTED BY THE GOVERNMENT- ThEY 

will be responsible for overseeing development of the 
facility- 
Called THE Ontario Waste Management Corporation, this 

COMPANY WILL BE INCORPORATED IMMEDIATELY- I WILL- SHORTLY 
INTRODUCE LEGISLATION TO SET UP A CROWN CORPORATION TO ASSUME 
MANAGEMENT AND DEVELOPMENT RESPONSIBILITIES- 



To HANDLE SHORT TERM NEEDS^ CONSTRUCTION WILL BEGIN AS 
SOON AS POSSIBLE ON THE SECURE LANDFILL SITE, A 
SOLIDIFICATION PLANT, A COMPLETE LAB AND SPECIAL STORAGE 
FACILITIES- The SITE WILL ULTIMATELY CONTAIN AN INCINERATION 
UNIT AND OTHER TREATMENT FACILITIES- 



142 



I ACCEPT THE MacLarEN RECOMMENDATION THAT THE SITE 
ITSELF WILL BE 100 ACRES IN SIZE WITH A BUFFER ZONE OF 640 

ACRES. Additionally, we are developing a further control 
zone of approximately one mile on all sides from the 
boundaries of the facility- 

Within the buffer zone around the site no residents will 
BE permitted- In the outer control zone we will welcome 

FARMING ON A LEASE-BACK BASIS TO DEMONSTRATE THE SUITABLE 
co-existence of THE SITE AND THE NORMAL ACTIVITY FOR THE 
AREA- 

I HAVE ADVISED THE CO^PROPONENTS AT ThOROLD AND HARWICH 
THAT WE ARE WITHDRAWING OUR PARTICIPATION FROM THE SHORT TERM 

PROPOSALS. This new site will replace the interim storage 

PROPOSAL FOR PCBs IN MiDDLEPORT AS WELL- We ARE OF COURSE 
prepared to meet ALL OUR LEGAL OBLIGATIONS- 



The South Cayuga site will be designed to handle the 
BULK OF Ontario's liquid waste- 



143 



Other points on this new facility; 

1- The waste management corporation will assist and 

SUPERVISE round-the-clock SECURITY- 

2. With the lab facilities in place^ no wastes will 
ever enter that site before the contents are fully 

KNOWN' 

3« There will be no radioactive material accepted- 

^. The Province will assume cost of upgrading and/or 
construction of the nec-:ssary roads to rf.duce 

transportation RISKS TG THE ABSOLUTE MINIMUM- 

5. The Ministry of the Environment will continue to 
fund research into alternative technologies. These 

TO BE incorporated WITHIN SITE WHERE APPROPRIATE. 



6. The site will be operated on a break-even basis- 

ThE user fees WILL ACT AS AM INCENTIVE TO ENCOURAGE 

industry to reduce. recycle or recuse their wastes- 
The Board will also investigate other ways to reduce 
waste volumes and encourage waste exchange 
programs- :/ 



144 



Mr- Speaker, let there be no doubt of the urgent need 
for this facility. (jur health and that of the environment 
depend on it- because of that need, 1 have come to another 
difficult decision- 

Since the final decision on site location and initial 
solidification technology is made, no hearing will be held 
UNDER The Environmental Assessment Act or The Expropriations 
Act on the few properties the government does not yet own- 

Much work must still be done to develop this facility. 
But 1 felt it necessary to inform the public as soon as it 
WAS possible to do so* 

Mr. Speaker, the cost of this facility is estimated at 
approximately $60 million. That is certainly high but the 
government feels that cost should not be the limiting factor 
when what we need is the best technology it is possible to 
establish- 

We are not able to look to other jurisdictions in Canada 

FOR any guidance WHATSOEVER- HOWEVER, AS SOON AS THE BOARD 
IS IN PLACE, I INTEND TO TOUR FACILITIES IN EUROPE WITH THEM 
SO THAT THEY CAN COPY OR IMPROVE WHERE APPROPRIATE, THE 
LATEST IN WASTE TREATMENT TECHNOLOGY, SO THAT WE MAY HAVE THE 
BEST FACILITY IN THE WORLD- 



145 



It is with some pride that I note the leadership role 
Ontario is taking in tackling this serious issue- And I 

FULLY INTEND TO KEEP IT THAT WAY- 



146 



Environmental Impairment Liability Insurance 

by 
G.T.G. Scott, Consulting Engineer 

The purpose of this paper is to report on j study undertaken for the 
Ontario Ministry of the Environment during 1979 covering the possible 
availability and use of Environmental Impairment Liability Insurance to 
cover exposures associated with the operation of waste disposal systems 
and facil ities. Hov/ever, Environmental Impairment Liabil ity Insurance 
being a relatively new type of cover with \/h1ch many people are 
probably unfamiliar, it v/ould appear appropriate to explain v/hat this 
insurance is and what cover it provides before going Into details of 
the actual study involved. 

Prudent management dictates that where an individual or organization 
is, in the course of their activities, exposed to a risk, then 
provisions should be made to ensure that funds are available to cover 
claims resulting from that risk or exposure- While larger 
organizations may provide reserve funds for such contingencies, or self 
insure, it is common practice to carry Comprehensive General Liability 
Insurance to cover the wide variety of risks to v^ich businesses are 
exposed. Historically such Comprehensive General Liability Policies 
contained no Environmental exclusion. In other words these policies 
covered the insureds liability for environmental damage resulting from 
their operations. 

In recent years public av^areness of the aesthetic and material damage 
resulting from discharges of materials to the environment, and claims 
for such damages, have increased in both frequency and magnitude. At 
the same time courts of law have progressively eased the path of the 
plaintiff attempting to obtain redress for damages whether real or 
imaginary. It is hardly surprising that insurers, faced with this 
situation, reacted in various ways to protect their interests. 

While marine risks are not the subject of this presentation it is 
probably worth noting the reaction in that area that follov/ed such 
incidents as that of the tanker the Torrey Canyon, Tanker ovmers took 
the initiative under the TOVALOP Agreement by voluntarily accepting 



147 



liability for coastal pollution arising from a tanker misshap. They 
have provided, with the assistance of insurers, the necessary financial 
guarantee for claims and clean-up costs. Similar agreements were 
subsequently made under OPOL for offshore oil operations. Thus, 
insurance cover for environmental impairment has been nad-i available to 
shipov/ners, charterers, salvors and offshore oil operators. 

Hov/ever, for the land based risks which are the subject of our current 
discussions the approach taken by insurers has been much more 
restricted. In general terms, while cover has been made available for 
environmental impairment liabil ity resulting from an accident, or 
sudden, unexpected and unintended happening, there has been a virtually 
unanimous refusal to accept similar exposures from "steady state" 
operations. In other works, while coverage for environmental damage 
resulting from "acute" conditions may be provided under a comprehensive 
general liability policy, damage resulting from "chronic" conditions is 
invariably excluded. 

While the attitude adopted by insurers towards landbased environmental 
impairment liability risks, as described above, may appear to be harsh, 
it is perhaps not unreasonable \/hen one considers the loss experience 
during recent years and the posture adopted by courts of law that has 
eased the path of plaintiffs. 

Fortunately, for those individuals or organizations whose activities, 
by their very nature, present an exposure to potential claims for 
environmental damage, the need for appropriate insurance cover was 
recognized by a group of European re-insurance companies. As a result 
of a meeting held in Paris in 1972, a plan for "total pollution cover" 
was developed and is now available worldwide to cover the legal 
liability arising from any form of environmental impairment, whether 
sudden and accidental or not. This coverage has been named 

"Environmental Impairment Liability Insurance." 

One might v/el 1 query \/hy the name environmental impairment was favoured 
for this insurance, rather than the shorter form "pollution". An 
examination of the definition of environmental impairment, as contained 
in the policy wording provides good reasons for the use of this term. 



148 



The policy states as follows:- "for the purpose of this policy, 
environmental impairment is defined as:- 

a) the emission, discharge, dispersal, disposal, seepage, release or 
escape of any 1 i quid, sol id, gaseous or thermal irritant, 
contaminant or pollutant into or upon land, the atmosphere or any 
water course or body of v/ater. 

b) The generation of smell, noises, vibrations, light, electricity, 
radiation, changes in temperature or any other sensory phenomena 
arising out of or in the course of the insured' s operations, 
installations or premises all as designated in the schedule." 

From the above, it should be obvious that the plan does indeed provide 
for "total pollution cover". 

It should be noted that the pol icy avoids the term "occurrence" and 
that the insurers will indemnify on a "claims made" basis. A claim is 
defined as "any single claim or series of claims resulting from one and 
the same isolated, repeated or continuing environmental impairment." 

The same comprehensive approach has been folloi/ed in defining the 
Indemnifiable effects of environmental impairment. Cover applies to 
claims, not only for personal injury (including death at any time 
resulting therefrom) and for property damage, but also for "impairment 
or diminution of, or other interference with any other right or amenity 
protected by law." The need for this extension becomes apparent v/hen 
one considers the potential for environmental suits brought for unusual 
reasons, such as the destruction of a scenic view, the obstruction of 
TV reception by a highrise building, the hampering of birdwatching by 
smog, or the impairment of recreational facilities by smelly or murky 
effluent. 

In addition to the compensation payments for damages, the policy also 
indemnifies for clean up costs incurred whether necessary as a result 
of legal obligation or to prevent an insured loss, and also pays for 
costs and expenses of litigation. 

As with any insurance cover, there are exclusions to this policy, which 



149 



fall under tv/o specific headings. 

The first type of exclusion includes those v/hich are absolute such as 
consequences of war risks, nuclear risks and claims from the insured's 
employees. An absolute exclusion also applies to fines, penalties and 
punitive damages. 

There is al so an exclusion which deal s with intentional acts. This 
excl usion has been careful ly worded so that it appl ies where an 
executive director ar any officer of the insured or any employee with 
specific responsibility for environmental control, is a\/are of non-com- 
pliance with any applicable regulation or instruction related to 
environmental impairment, issued by a competent authority. However, 
the cover does remain in force if the insured is operating under 
conditions of non-compl iance with the consent of the jurisdictional 
authority and with the intent to comply as soon as can reasonably be 
expected. In a way this is a good faith clause v/ith the insured and 
the insurer working together. 

Further excl usions are inserted in the pol icy on a optional "buyback 
principle". These include environmental impairment involving a sudden, 
unintended and unexpected happening; vehicles; water craft; oil or gas 
drill ing platforms; deep \^ater ports; aircraft or airport operation; 
product liability; genetic damage; damage to the insured's property or 
property in his care, custody or control ; and joint liabil ity with 
others. Under appropriate circumstances it may be possible to amend or 
delete one of more of these exclusions when coverage is not otherwise 
available to the insured. So far as sudden, unintended and unexpected 
happenings are concerned, for most insureds, these events are covered 
under their C6L policies and the exclusion only operates to prevent 
overlapping coverage. However, some insureds, especially those 

utilising certain hazardous operations, may no longer be provided this 
coverage under their CGL policy. For those firms, EIL insurance 
provides valuable protection. 

Since actuarial information relating to environmental impairment 
1 iabil ity claims is still virtually nonexistant, risks are rated by 
reference to a rating manual based on an analj^ical approach. In addi- 



150 



tion to quantifying what might be called the static risk elements, by 
reference to this rating manual, there are a number of variable factors 
which insurers must take into account vihen rating any individual 
operation. These incl ude the size of the insured's business, the 
extent of pollution already present in the surrounding environment, 
methods employed for waste disposal, past record of claims, degree of 
r i sk av/areness on the part of pi ant management and staff, and the 
qual ity of internal housekeeping. Al so to be numbered among the 
variable factors are the strictness of standards laid dov/n by authority 
for the industry or area concerned, the relative effectiveness of 
enforcement agencies, the type of liability imposed by statute and the 
practice of the courts relating thereto. 

Each risk is therefore the subject of a technical assessment or survey 
by independent scientific consultants. While the survey is commission- 
ed by the insured, a portion of the first years premium is rebated to 
the insured to assist in paying all or part of the cost of this report 
if environmental impairment cover is subsequently purchased- 

With this background as to the nature and operation of the Enviromental 
Impairment Insurance program, the project undertaken for the Ontario 
Ministry of the Environment can be reviewed in a clearer light. 

The purpose of the project v/as to examine the ava ilabil ity of this 
insurance to cover certain aspects of the operations of waste 
management systems and v/aste disposal operations and to ascertain the 
terms under which the insurance would be made available. In addition 
preliminary cost estimates ivere obtained based on tvTO specific waste 
disposal operations in the Province. Reference v/as made during the 
course of the study to the Interim Report on Perpetual Care for Waste 
Management Facilities prepared by the Perpetual Care Task Force of the 
Ministry of the Environment. This document sets out the type and 
extent of liability insurance \/hich may be required to provide off-site 
protection for third parties- 
Discussions viere held with representatives of the managers of the 
insurance program, H. Clarkson (Overseas) Limited in London, England, 



151 



from which it was established that Environmental Impairment Liability 
Insurance as described above is in fact available to provide the 
liability cover under consideration. Such cover is available to the 
ovffiers, operators and users of waste nanagement systems and v/aste 
disposal sites, as a means to ensure that such parties are in a 
position to meet their financial obligations in the event that claims 
are made by third parties whose interests are damaged by the operations 
involved. 

Of particular interest was the reaction of the insurers to the request 
for similar cover for operations involving the handling, treating and 
otherwise disposing of 1 iquid, hazardous , hospital and other simil dr 
types of waste which might be considered "special" in nature or 
presenting "unusual" environmental hazards. There again the response 
was positive, although the provision of insurance for such facilities 
will be considered on a case by case basls- 

Non-binding "Premium Indications" and details of applicable limits and 
deductibles are_ readily available from the Insurers through Canadian 
Insurance Brokers on submission of certain basic Information. Thi s 
information comprises details of the ovmer or operator of the facility. 
Its location and history, the processes and operations involved, data 
concerning compl iance v/lth regulatory requirements and of course 
particulars of any Incidents or claims that have occurred involving 
environmental impairment. Where available or applicable financial 
information is also required together with details of other liability 
Insurance coverage carried. These Premium Indications are non-binding, 
are normally valid for a period of six months, and are subject to the 
preparation of the technical evaluation referred to above. 

Subsequent to the receipt by the insured of the technical evaluation 
knov/n as an Environmental Risks Analysis Report, a firm "Premium 
Quotation" is provided by the Insurers. 

The general form and provisions of the cover has been described above. 
The Basic Policy Wording is set out in form EIL (CAN) 1279 v/hich Is 
available through Brokers. The actual policy wording for a specific 
risk can, within certain defined 1 imits, be written to provide for 



152 



Specific requirements associated with individual risks. 

The policy is» as previously noted, written on a "claims made" basis 
and is for a tv/elve month policy period. Renewal is subject to a 
technical "renewal" report which is prepared and paid for by the 
insurers. 

Bearing in nind the fact that many environmental incidents invol ving 
v/aste disposal sites have in fact occurred subsequent to the active 
life of the site in question, the subject of a "discovery period" was 
of major concern in the study. Here again the response of the insurers 
has been generally posi ti ve- They have indicated a wi 1 1 ingness to 
provide for a discovery period of up to five years, although this will 
probably require consideration on a case by case basis particularly as 
regards the additional premium that will undoubtedly be involved. 

In the ownership, operation and use of a waste disposal facility, a 
number of different parties are often involved, each of whom may have 
an insurable interest in the facility or operation. A policy can be 
written to cover such an eventuality, each such party being a named 
insured. Also the policy can, subject to the approval of the insurers, 
be transferable to a new ov/ner or operator, or be extended to cover the 
interests of additional parties. 

It is not uncommon for Group Insurance Programs to be developed to 
cover associations or groups of individuals or organizations having 
similar occupations or interests- It is understood that the insurers 
would be willing to consider such an approach should Legislation or an 
increasing av/areness of the liability exposures involved result in a 
more general demand for this type of insurance. It is perhaps worthy 
of note that a Group Insurance Plan for truckers has in fact been 
established by a Truckers Association in the United States. Also a 
Group Insurance Program is in place in Canada to provide this type of 
Insurance to municipal ities- 

Follov/ing a review of the premium Indications received for two specific 
operations, it was requested by officials of the Ministry of the 
Environment that information be assembled to provide some preliminary 



153 



indications of the possible financial impact if all municipal disposal 
sites in the Province v/ere required by law to carry the insurance 
described. 

With the assistance of the insurers a rating system v/as developed based 
on size of municipality on a population basis. These rates are the 
maximum per capita insurance rates that v/ould normally be applied to 
sanitary landfill operations involving domestic and commercial solid 
v/astes only. The disposal of liquid, hazardous, hospital and other 
simil ar types of waste was specif ically excl uded. These rates were 
then appl ied to the population statistics in the 1977-78 Municipal 
Directory published by the Ontario Ministry of Treasury, Economics and 
Intergovernmental Affairs. The 1 imits of Liabil ity used \iere 

$1,000,000 for any one claim with an aggregate of $2,000,000 in any one 
year or policy period. Deductibles varied from $2,500 for the smaller 
municipal units to a maximum of $25,000. No allowance was made for a 
discovery period, and incidents involving sudden and accidental 
occurrences were assumed to be covered under appropriate comprehensive 
general liability insurance- 

The Municipal Directory provides statistical classifications of the 
municipalities by Upper Tier (metropolitan, regional, district, 
counties, regions) and the Lov/er Tier (cities, boroughs, separated 
towns, tov/ns, villages, tov/nships, improvement districts). The per 
capita premium rates referred to above v/ere applied to both these sets 
of statistics and the total premiums calculated were in round figures 
as follov/s:- 

Based on Upper Tier Municipal Classifications $697,000 

Based on Lov/er Tier Municipal Classifications $1,801,000 

The wide spread in these two figures reflects the higher per capita 
insurance rates applicable to smaller municipal units which predominate 
in the Lov/er Tier Classification. In actual practice insurance cover 
would most likely be carried by municipalities in the Upper Tier 
Classification, to v/hom responsibility for solid waste disposal has in 
many cases been assigned. It v/ould therefore be reasonable to assume 
that, based on the factors enunerated above that have been used in 
these calculations, the actual total costs would be in the order of 



154 



Si. 25 million. A further reduction in this amount could be achieved if 
the environmental risks associated with some of the major disposal 
operations prove such as to permit the use of lov«r per capita premium 
rates. 

Limits in excess of the $1M/2M used for the above calculations are 
available through the Environmental Impairment Liabil ity Insurance 
program up to $10M/20M. Limits in excess of these figures are subject 
to special negotiations. 

The deductibles referred to are the minimum normally available to the 
various sizes of municipality. The use of higher deductibles will 
normally result in loi/er premiums. 

As noted, these premiums do not provide for a five year period of 
discovery as the premium loading to cover this requirement will vary 
depending on site specific conditions. 

The above provides a brief summary of the study undertaken for the 
Ministry of the Environment. For a more detailed explanation of the 
insurance program described, reference should be made to available 
literature v/hich describes in detail its history, development, and the 
Insuring agreement. 



155 



INVESTIGATIONS OF SUBSURFACE CONTAMINANT MIGRATION IN SAND AQUIFERS 

AT LANDFILL SITES 



John A. Cherry 

Department of Earth Sciences 

University of Waterloo 

Waterloo, Ontario 

N2L 3G1 



ABSTRACT 



During the past five years the Hydrogeological Research Group 
at the University of Waterloo has been investigating the processes of 
subsurface contaminant migration at several landfills. This paper 
provides a suimiary of the results obtained at three landfill sites 
located on permeable sand aquifers in Ontario. The oldest of these 
landfills began operation in 1940 and was abandoned in 1976. The 
other two sites began operation in 1960 and 1970 and are still active. 
At each site a zone of contaminated groundwater has moved a distance 
of 700 to 800 m from the landfill. At two of the sites, the contamina- 
ted water has remained entirely below groundsurface. At the third 
site, contaminated groundwater feeds springs that drain into a local 
stream. The plumes of contaminated groundwater are characterized by 
concentrations of chloride, bicarbonate, sodium, calcium, magnesium, 
iron, and dissolved organic carbon at levels well above background 
concentrations. Processes of attenuation 1n the aquifers cause each 
of these constituents to decline considerably in concentration in the 
directions of groundwater flow. Toxic heavy metals and non-metals 
such as arsenic and selenium have not been observed in the plumes at 
two of the sites; insufficient data on these constituents is 
available from the third site. There is no indication at present that 
the plumes have caused significant degradation of water resources used 
by man; however, little is known about the composition or effects of 
organic compounds that comprise the dissolved inorganic carbon. 



156 



INTRODUCTION 

In recent years in Ontario and in many other parts of North 
America, the selection of sites for sanitary landfills has become a 
controversial issue. Much of the controversy that is associated with 
many new sites pertains to actual or perceived hazards related to the 
possibilities of off-site movement of landfill-derived contaminants in 
groundwater. This concern is most relevant in the humid or sub-humid 
climatic regions of North America because in these regions water from 
rain and snow infiltrates through the landfill refuse and cofmonly 
causes leachate to seep from the landfill into the underlying ground- 
water regime. 

Nearly all sanitary landfills in Ontario are situated on 
Quaternary deposits that were deposited during the Pleistocene Epoch 
by glaciers or by rivers or lakes formed by glacial meltwater. These 
deposits can be grouped in four main catagories: gravel, sand, silt 
and clay. When landfills are situated on deposits that are composed 
of clay and silt (such as clayey or silty glacial till or glacial 
lacustrine clay), there is generally little possibility of extensive 
migration of contaminants in groundwater. This is the case because 
groundwater flow in these deposits is generally very slow. When land- 
fills are located on deposits of sand or gravel, however, groundwater 
flow rates are commonly high (from tens of centimetres per day or to 
many metres per day) and landfill-derived contaminants may move large 
distances beyond the site boundaries in the groundwater zone. Because 
rain and snowmelt infiltrate through landfills even after the landfills 
are covered over with earth and are seeded to grass or trees, leachate 
continues to be produced after they are abandoned. Zones of ground- 
water contamination can undergo expansion for many decades or even 
hundreds of years. 

The purpose of this paper is to provide a brief overview of 
some of the results of investigations of contaminant occurrence and 
migration of contaminants in groundwater at sanitary landfills 
situated on deposits of permeable sand in Ontario. These investiga- 



157 



tions, which are being conducted by the University of Waterloo with 
funding now provided mainly by the Ontario Ministry of the Environment 
began in 1976 at an abandoned landfill at the Canadian Forces Base at 
Borden, Ontario, and in 1980 were extended to include the landfill 
that serves the city of North Bay and the Woolwich landfill near Elmira 
in the Regional Municipality of Waterloo. The objective of these 
investigations is threefold: 1) to develop improved methods for monito- 
ring contaminant migration in groundwater at landfills, 2) to develop a 
better understanding of the physical and chemical processes that cause 
attenuation of landfill-derived contaminants in groundwater and 3) to 
appraise and develop models for prediction of contaminant migration in 
permeable sandy deposits. 

DESCRIPTION OF THE STUDY SITES 

The development of extensive zones of contaminated groundwater 
at landfills normally takes many years or decades and thus little can be 
learned by monitoring a new landfill for only a year or two just after 
landfilling begins. An alternative approach that we are pursuing is the 
monitoring of groundwater zones that have been receiving landfill 
leachate for many years or decades so that the long-term effects on 
groundwater can be determined by only a few years of monitoring. 

To date, the investigation has included three landfills, 
referred to as the Borden, North Bay and Woolwich landfills. The land- 
fills differ considerably in age and size but they are not much different 
in refuse thickness. At each site the refuse is situated in unconsolida- 
ted sand. At the Borden and North Bay sites the bottom of the refuse is 
near or just slightly below the water table. At the Woolwich site the 
bottom of the refuse is 5 to 10 m above the water table. At each site 
sand excavated from the site or from nearby areas was used to cover the 
refuse. Landfilling at the Borden site began in 1940 and ceased in 1976, 
at which time the landfill received a final sand cover that was seeded 
with grass. The North Bay and Woolwich landfills began operation in 



158 



1960 and 1970, respectively, and they are continuing to receive refuse. 
Nearly all of the landfilled areas at these sites are at their final 
levels and have received sand cover. Part of the landfilled area at 
the North Bay site has also received sewage sludge and sawmill cuttings. 
The permeable sand cover on each of the landfills and the flat or only 
gently sloping surface over much of the landfilled areas are features 
condusive to infiltration of water from rain and snowmelt through the 
refuse. This causes leachate to move downward to the water table. 

The Borden landfill received normal household and cafeteria 
wastes and building construction debris from the Canadian Forces Base 
Borden which, until 1976, the landfill served as the only operational 
dump site during the post World War II period. 

METHODS OF INVESTIGATION 

Field studies at the Borden site included geological test 
drilling, stratigraphic coring, geophysical surveys, installation of 
conventional piezometers and standpipes, installation of multilevel 
point samplers and bundle-type multilevel piezometers, periodic water- 
level and water-quality monitoring, and groundwater-temperature surveys. 
These investigations are described in detail by Waterloo Research 
Institute (1980). Similar investigative techniques were used at the 
Woolwich and North Bay sites, with the exception of stratigraphic 
coring and geophysical and temperature surveys. To date, the Woolwich 
and North Bay sites have been monitored in less spatial detail and less 
frequently than the Borden site; however, the investigations at these 
two sites will continue for one or two more years, whereas the investi- 
gation of the Borden landfill is nearly complete. 

In the initial phase of groundwater monitoring at two of the 
sites (Borden, 1974-75; Woolwich, 1975) conventional standpipe piezo- 
meters and water-table standpipes installed using hollow-stem augers 
were used. Based on this experience it was concluded that more cost- 
effective monitoring devices were needed to achieve detailed three- 



159 



dimensional monitoring of the water chemistry in the sand aquifers at 
each site. Several groundwater monitoring devices were then develop- 
ed or adapted for the investigation, two of which are shown in Fig. 1. 
The multilevel point sampler is described in detailed by Pickens et al. 
(1978). The bundle-type piezometer is described by the Waterloo 
Research Institute (1980). 

The multilevel samplers shown in Fig. 1 enable water samples 
to be acquired from different levels at a single borehole in a sand 
aquifer. Each of these monitoring devices consists of a cluster of 
polyethylene or polypropylene tubes attached to a PVC pipe, either 
inside or outside the pipe. Each tube in the cluster extends to a 
different depth below the water table so that when the cluster of tubes 
is sampled by vacuum pumping, a vertical profile of chemical composition 
can be obtained at the monitoring site. At sites where the water table 
is deeper than the limit for suction sampling, the bundle piezometers 
are sampled using a narrower tube and check valve as a bailer. 

At each of the landfills, networks of multilevel point samplers 
and/or bundle piezometers were installed in stages. During each stage a 
number of the devices were installed and then sampled so that information 
on location of the zones of contamination was obtained. Upon evaluation 
of the concentration patterns, appropriate locations were selected for 
installation of monitoring devices in the next stage of drilling. By 
staging the installation program for monitoring devices in this manner, 
the monitoring networks that were developed after several stages provided 
more detailed information on the contaminated zones than would otherwise 
have been the case. 

Each monitoring site with a multilevel point sampler or a 
bundle piezometer has between nine and 25 sampling points. With many of 
these devices at each landfill site, the total number of sampling points 
at each site is large. All of the sampling points were sampled and 
analysed for electrical conductance and chloride, both of which can be 
done quickly at low expense. At each of the sites, these two parameters 
provided a indication of the presence or absence of leachate contamina- 
tion in the aquifer. After delineating the general patterns of contami 



160 



nation in the sand aquifers, a representative group of sampling points 
at each site was sampled for analysis of a large number of dissolved 
inorganic constituents, including major ions, minor constituents, and 
trace elements. When these samples were collected, the water was 
filtered as soon as it was withdrawn from the aquifer. Samples for 
cation and trace element analyses were then immediately acidified to 
prevent chemical changes prior to laboratory analysis. The analyses 
of samples from the Borden and North Bay sites were conducted in the 
water quality laboratories of the Ontario Ministry of the Environment. 
Samples from the Woolwich site were analysed in the laboratories of 
The Regional f^nicipality of water. 

PATTERNS OF GROUNDWATER CONTAMINATION 

The occurrences of contaminated groundwater, identified by 
electrical conductance and chloride concentrations, in the sand aquifers 
at the three sites are shown in plan view and along cross sections in 
Figures 2-7. The data upon which the Borden diagrams are based are 
presented by MacFarlane (1980) and by the Waterloo Research Institute 
(1980). The data pertaining to the Woolwich and North Bay sites will 
be included in reports and theses that will be prepared in 1981 and 
1982. 

At each of the sites a plume of contaminated groundwater 
originates at the landfill and extends a distance of 700 to 800 m in 
the direction of the regional water table slope. Each of the contamin- 
nant plumes travels along the bottom of the aquifer. Deeper movement 
of the contaminated water is prevented by deposits of glacial till or 
glaciolacustrine clay that have a much lower hydraulic conductivity than 
the aquifers. The Borden plume is fan-shaped because during the spring 
and early surrmer, mounding of the water table beneath the landfill 
causes groundwater flowlines to extend in a radial pattern from the land- 
fill. In contrast, the North Bay and Woolwich plumes are narrow because 
of the lack of extensive influence of water-table mounding beneath the 



161 



landfill and because of the uniformly sloping regional water table. 

The position of the front of the plume at the Borden site 
(Fig. 2) is well-defined because numerous monitoring devices are 
located in the vicinity of the front and because the monitoring devices 
were sampled on various occassions during 1977-1980. The average 
northward velocity of groundwater in the aquifer in the vicinity of the 
plume front is approximately 50 to 75 metres per year. Comparison of 
concentration patterns for several years suggests, however, that the 
identifiable plume front is advancing at a much slower rate. This 
condition is attributed to mixing (dispersion), which causes the plume 
to dissipate as it advances. 

At the North Bay site the leachate springs located near the 
stream about 800 m southwest landfill probably represent the front and 
exit zone of the plume. Although a definative interpretation cannot 
be developed at present because there are insufficient monitoring 
devices in the vicinity of the springs, it appears that the plume will 
advance no further. 

At the Woolwich site the plume has been traced southward for 
a distance of about 800 m from the landfill. The front of the plume 
however, has not yet been delineated. It is expected that this will 
be accomplished in the next stage of installation of monitoring devices. 
The existing data indicate that the plume has undergone considerable 
attenuation along the 800 m of travel distance. In comparison to the 
Borden and North Bay sites it is much more costly and time-consuming to 
accurately delineate the plume at the Woolwich site because the depth 
to the bottom of the aquifer is much greater, thereby causing greater 
drilling costs, and because the depth to the water table is also much 
greater, which causes water sampling to be much more tedious. 

WATER QUALITY IN THE CONTAMINATED ZONES 

In terms of percentage of the total dissolved solids in the 
contaminated zones at the three sites, the dominant inorganic 



162 



constituents are chloride, bicarbonate, sodium, calcium, magnesium, and 
iron. The Borden site differs from the other two sites in that sulfate 
is also a major component of the dissolved solids. Although these 
major inorganic species cause the water to differ considerably from the 
natural groundwater in the aquifers and although some of these species 
cause the water to be unsuitable for domestice use, they are not toxic 
to humans and they do not represent an appreciable hazard to the 
biosphere. If water qualtity is judged on these constituents alone, 
it would be reasonable to conclude that there are many other activities 
of man that cause groundwater to become as unpotable as at these land- 
fills but over much larger areas than is affected by landfills. 

Numerous groundwater samples from the Borden and North Bay 
sites were analysed for heavy metals and other hazardous inorganic 
constituents such as arsenic, selenium, and fluoride. We have found 
no evidence to indicate that the plumes contain any toxic metals or 
non-metals at concentrations that generally exceed the limits recom- 
mended by provincial or federal guidelines for drinking water. It is 
reasonable to conclude that these constituents are not being leached 
from the refuse at significant rates or that they are being removed 
from the leachate by geochemical processes in the sand imnediately 
beneath the landfills. This may be occurring as a result of precipi- 
tation, co-precipitation, and adsorption. Insufficient data are 
available at the present time to determine whether toxic metals or 
non-metals at the Woolwich site occur in the contaminant plume beyond 
the site boundaries. 

In addition to the analyses of numerous dissolved inorganic 
species in the contaminated groundwater, the samples were analysed for 
total dissolved inorganic carbon (DOC). Each of the plumes has DOC 
concentrations that are considerably above background concentrations 
in the aquifers. The elevated concentrations extend throughout the 
plumes with declining concentrations towards the frontal positions of 
the plumes. The dissolved organic carbon has probably been derived 
from food wastes, plastic manufactured materials, and possibly liquid 



163 



industrial wastes. Investigations have recently been initiated with a 
view to identifying many of the organic compounds that comprise 
selected fractions of the dissolved organic matter. Until the nature 
and toxicity of the dissolved organic matter in the contaminant plumes 
is known, it will not be possible to assess potential long-term 
environmental effects of landfilling at sites located on sand or gravel 
aquifers in areas where groundwater pumping occurs or where groundwater 
feeds surface water courses. 



DISCUSSION 

The results obtained from the investigations of the three 
landfill sites indicate that landfills on sand aquifers can produce 
zones of contaminated groundwater that extend many hundreds of metres 
beyond the site boundaries. As the fronts of the contaminant zones 
advance, mixing (i.e. dispersion) causes the concentrations of the 
dominant constituents in the plume to decline considerably. The 
results obtained from the Borden site suggest that in some cases mixing 
may cause the plume to dissipate to the extent that the rate of advance 
becomes very slow relative to the rate of groundwater flow. 

At the Borden and North Bay sites, no water-supply wells 
exist in the aquifers through which the plumes are moving. At the 
Borden site, water-supply wells are located in deeper aquifers that 
are isolated from the shallow aquifer by extensive clay beds. At the 
North Bay sites local wells are in bedrock and the population pattern 
is such that the zone of groundwater contamination is of no consequence 
at present. At the Woolwich site, no water-supply wells have been 
affected by the plume. Studies are underway to determine whether any 
of the existing wells in the rural area may be affected at some time in 
the future. 

At all three sites, zones of contaminated groundwater have 
migrated a considerable distance from the boundaries of the landfill 
areas. In terms of the criteria that are coimonly used for assessing 



164 



landfill sites, the sites can be judged to be inappropriate for land- 
filling. 

To avoid offsite movement of leachate in groundwater, many 
of the new landfills that have been developed in Ontario in recent 
years are situated on clayey deposits. Because of the climatic 
conditions that exist in Ontario and the nature of soil material often 
used for cover material, leachate normally forms in these landfills. 
Because the leachate cannot seep rapidly into the underlying clayey 
geological deposits as would occur at sandy sites, leachate mounding 
and side springs will develop unless the landfill design includes 
leachate collector drains, sumps, or pumps and provision for leachate 
passage to municipal sewage treatment plants or to other discharge 
points to rivers or lakes. If the leachate that is collected from the 
landfill is routed through a sewer system to a sewage treatment plant, 
many of the constituents in the leachate pass through the plant with 
little or no degradation. From the plant, they enter lakes or rivers. 
If this approach to landfill and leachate management is adopted, 
sewage treatment plant capacity is utilized and must continue to be 
utilized for many decades or hundreds of years in order to avoid 
direct discharge of leachate to the environment. 

When appraising options for landfill siting in Ontario, it is 
appropriate to recognize that offiste movement of leachate is generally 
unavoidable and that the movement can occur by way of leachate drains, 
collector systems, ditches, and then by way of sewers to sewage plants 
or directly to surface waters. Or the offsite movement can occur via 
the groundwater zone to surface water, or to water supply wells. 
Regardless of the approach taken, there will eventually be a flux of 
landfill - derived contaminants to the biosphere. 

In this context it is interesting to re-consider the results 
of the investigations of the three landfills reported on in this 
paper. Landfilling at the Borden site conmenced 40 years ago and yet 
since this time leachate has not had any influence on surface water 
and there is little possibility that it ever will significantly 
influence surface water. The plume has influenced groundwater quality 



le*'^ 



but because alternative aquifers are availabe for water supply, this 
influence has had no affect on the local population. It probably never 
will as long as the shallow aquifer is not chosen for any consumptive 
use. 

The North Bay landfill has caused contaminants to move 
through the aquifer and, after considerable attenuation, enter the 
local surface water drainage system. The sand aquifer has, in a sense, 
performed the same function as a sewage treatment plant, except that it 
has probably 'treated' the water to a greater degree. Unfortunately in 
esthetic terms offsite movement of leachate in the aquifer has caused 
degradation of some parts of the surface environment in a land area 
that is at present not owned by the owner of the landfill. If the land 
area to the south and southwest of the landfill had been originally 
included as part of the landfill site, the overall consequences of the 
subsurface migration of contaminants to the local springs and seeps 
could conceivably have been regarded as a favorable form of water 
treatment. An uncertainty that currently exists in this regard relates 
to the dissolved organic compounds in the seepage. Until the organic 
matter is adequately characterized, there will continue to be some 
uncertainty with respect to the potential for the contaminated seepage 
from springs to have an adverse influence on the local stream. 

At present less is known about the water quality in the plume 
at the Woolwich site and of the potential for the plume to eventually 
advance into areas where water-supply wells currently exist. If the 
plume follows a pathway that does not intersect existing wells, then 
it will probably have no significant environmental consequence, even 
after many decades or longer. 

SUftlARY AND CONCLUSIONS 

At each of the three landfill sites reported on in this paper, 
a plume of contaminated groundwater has moved in the sand aquifer many 
hundreds of metres from the site boundaries. The dominant dissolved 



166 



constituents in the plumes are chloride, bicarbonate, sodium, calcium, 
magnesium and iron. Heavy metals and non-metals have not been identi- 
fied at hazardous concentration levels in the plumes at the Borden and 
Woolwich site. Insufficient data is available on these constituents 
at the Woolwich site. At each of the sites, dissolved organic carbon 
at concentrations above background occurs throughout the plumes. 
Investigations aimed at identifying many of the organic compounds that 
comprise this organic matter have recently been initiated. 

ACKNOWLEDGEMENTS 

Numerous faculty members, technicians and graduate students 
have participated in the investigations of the landfill sites described 
in this paper. Those that were involved in the Borden investigation 
are authors and co-authors of papers in the Waterloo Research Institute 
(1980) volwne listed below. The results of the Woolwich and North Bay 
studies are as yet unpublished. The investigations of these two sites 
have been undertaken primarily by Paul Buszka, Janet Hewetson, Paul 
Johnson and Scott King. 

Financial support for these studies has been provided by 
The Ontario Ministry of the Environment and by Environment Canada. 



REFERENCES CITED 

Pickens, J.F.. J. A. Cherry, G.E. Grisak, W.F. Merritt. and B.A. Risto, 

1978. A multilevel device for ground-water sampling and 

piezometric monitoring, Ground Water, Vol. 16, No. 5, 
p. 322-327. 

Waterloo Research Institute, 1980. CFB Borden Landfill Study, Vol. 1, 
Hydrogeological Studies of A Sandy Aquifer A. An abondoned 
Landfill (this volume comprises eight chapters by different 
authors) . 




^ 



iSmm fO 
20mm 00 

Bnwn ID 
I2mni00 



POLY-TUBrNG 



erNOING TAPE 




EPOXY CEMENT 
PLUG 



PERFORATED INTERVAL 
WITH NYljON SCREEN 



PVC PIPE 

-SLOTTED INTERVAL 
WITH NYLON SCREEN 

-END CAP 



-END CAP 



COUPLINGS 




—PVC PIPE 



STAINLESS 

STEEL 

SCREEN 



-SAMPLER POINT 



-END CAP 



Figure 1 



Schematic diagrams of a bundle piezometers and a multilevel 
point sampler. 







METRES 
100 



100 



MULTILEVEL SAMPLER 
<D BUNDLE PIEZOMETER 
2220^ WATER TABLE ELEVATION 
•^■"^ EXTENT OF CI CONTAMINATION 



Figure 2. Area of contaminated groundwater, water-table contours, and 
sampling sites used in detailed hydrogeochemical studies at 
the Borden landfill. 



as 

00 




200 400 H. 

Horizontal Scale 



— 50— mg/l 

*■ Standpipe Tip 

o Piezometer Tip 

• Multi - level 
Sampling Point 

▼ Water Table 

3 Clay 



"^"" '■ ?hS"thrBi^!;^:^i^^ ^^""^ ^ ^-^^^"''^-^ -0" -ction 






n 



170 



LEACHATE 
SEEPAGE AREA 




LEACHATE SPRNGS 



Figure 4. Area of contaminated groundwater and other hydrologic features 
at the North Bay landfill. 



GRCXJNDWATER CONTAMINATION 
NORTH BAY LANDFILL 




BEDROCK 



metres 



Figure 5. Zone of contaminated groundwater and leachate springs displayed 
on^a longitudinal cross section through the North Bay landfill 






172 



FIELD 





«.A 



FOREST 



FIELD 



200 



metres 



Figure 6. Area of contaminated groundwater at the Woolwich landfill in 
the Regional Municipality of Waterloo. 



SE 



LANDFILL 



NW 



ROAD 




SAND 



BEDROCK 



M 

rO 

-10 
-20 
-30 
-40 
-50 

•60 

-70 
-80 




200 



metres 



Figure 7. Zone of contaminated groundwater displayed as a longitudinal 
cross section through the Woolwich landfill. 






174 



ORGANIC CONTAf-lINANT REMOVAL IN DRINKING 
WATER - AN OVERVIEV; 



By: 

K.J. Roberts 
Water Technology Section 
Pollution Control Branch 
Ontario Ministry of the Environment 



Nov. 25/RO 



in 



ORGANIC C0NTA:1INANT REMO^'AL in IIRTNKTtJG 
VJATKR - AN OVERVII'VJ 

K. J . Roberts 



1. INTRODUCTION 



Preamble 



The results of surveys of trace orqanics in drinking water (1-3), 
epidemiological surveys associating such organics with increased 
cancer risk (4) , and the recently published guidelines for Canadian 
Drinking Water Quality, 1978,(5) which contains a guideline for tri- 
halomethanes, and the regulations promulgated by the United States 
Environmental Protection Agency (6) have all contributed to an in- 
creased interest in methods for evaluating a water supply and its 
exposure to organic contaminants. The risk associated with the 
presence of organic contaminants in a drinking water (7) and the 
determination of appropriate methods for treatment have consequently 
received considerable attention (8,9) . 

General 



The organic compounds that have been identified in drinking 
water make up a small fraction of the total organic matter present. 
About 90% of the volatile organic compounds have been identified and 
quantified but these represent no more than 10% by weight of the total 
organic material. Only 5-10% of the non-volatile organic compounds, 
that comprise the remaining 90% of the total organic material, have 
been identified. 

More than 700 specific organic chemicals have been identified 
in various drinking water supplies. These compounds result from 
such diverse sources as industrial and municipal discharges, urban 
and rural runoff, and natural decomposition of vegetative and animal 
matter, as well as from water and sewage chlorination practices. Com- 
positions and concentrations vary from virtually nil in protected 
groundwater to substantial levels in many surface waters and contaminat- 
ed groundwaters . 



176 



Orqanic clV'-^mical c"'.>iit'?inii-ian.t:j in a r unking u-alc i. can b,; divid':d 
into two major elass-ii^s : those o': natural origin arrl th.'^cc of nynV.h- 
etic orig.'-n. The nat-ural oulT^tancp-H represent by far the firoatoi-^t 
portion and consist primarily of undefined humu'j and fulvic mater- 
ials anu others proaucea by normal organic aecomposiELun or oioric 
transformation and are not known to be harmful in tliemsalves. There- 
fore it will be useful to focus attention on those organic chemicals 
of synthetic origin . 

The synthetic chemicals in water r3,n be sub-divided into two 
groups, the first group consists of those chemicals that result from 
water treatment practices (eg. trihalomethanes) (10). Recent studies 
indicate that except for certain cases trihaloxethones constitute 
the largest portion of the identifiable synthetic chemicals in drink- 
ing water. Unlike other synthetic chemicals, chloroform and other 
trihalomethanes are formed during the treatment process. They are 
thus found in virtually every drinking water supply that is disinfected 
by chlorine, and not uncoinmonly at concentrations i.n the hundreds of 
parts per billion. Studies have indicated that the trihalomethanes 
may represent only a portion of the total halogenatcd products of 
chlorination of water (11). Methods are being develoised to quantify 
the total halogenated organic compounds produced during chlorination; 
however for other than the chlorinated phenols and a few other sub- 
stances, identification is very difficult. 

Halogenated organics such as carbon tetrachloride, chloroform and 
hexachloroethane have also been detected as parts per million levels 
as contaminants in chlorine. The method of manufacture of the chlorine 
determines the levels of contarT-ination. It is obvious then tlie chlor- 
ine used for potable water disinfection must be of the highest purity 
to avoid introduction of contaminants into drinking water. 

The second group of synthetic chemicals consists of those chem- 
icals introduced as a result of point and non-point sources of pollution. 
Tlirougliout Nortli Araoriea lioth surface waters and to a lesser degree 
groundwaters are rontisminanted with a variety of these pollution related 
syntht tic organic ch-^micals ranging from the lower molecular weight 
halogctiattHl hydrocarbons, and luonocycli.c aromatic compound."; to higher 
mol'. ■■-■1.1'} ru: v.'-'' ■' rMi. ;V'-:S-I\it:ld.('^i-; ,- pol yt^yrllt,' aTtnaati.c L-')r\i_JOiin.-l,i . 



177 



The above classes oC coir-pounds havo been found in drinking 
water using qas chroruotography or gas chromotography/rnass spectro- 
scopy. However, many of th'- natural products and also high molecular 
weight synthetics in I'j.iter are not amoncible to detection by these 
commonly used methods. As mentioned before the organic contaminants 
which have been identified in drinking water constitute only a small 
percentage of the total amount of organic matter present. 

Risk Assessment (12) 

The hazards of ingesting chemical pollutants in drinking water 
can be assessed in two general ways: with epidemiological studies 
and with laboratory studies of toxicity. The aim of both types is 
to provide information on the risk to man. For such an asjsessement 
the average amount of water consumed per person is generally assumed 
to be two litres/day. The daily consumption of water however is a 
function of such factors as temperature, humidity and physical 
activity; these factors may vary widely. 

Concerning the toxicity to man, there are certain principles 
which should be borne in mind when efforts to assess the effects of 
long continued exposure to chemical trace contaminants at low dose 
rates are made. Firstly, it is assumed that effects in animals, 
properly qualified, are applicable to man. Secondly, we do not now 
have methods existing to establish a threshold for the long term 
effects of toxic agents. Thirdly, that the exposure of experimental 
animals to toxic agents in high doses is a necessary and valid method 
of discovering possible carcinogenic hazards in man. And fourthly, 
that exposure to such chemical compounds should be assessed in terms 
of human risk, rather than as safe or unsafe. Risk only constitutes 
half of the essential comparison that should be made in the assessment 
of human hazard; the other half is the benefit to the exposed populat- 
ion of the agent for which hazard has been identified. It is not 
possible to guarantee a risk free society; nor is a risk free society 
necessarily the best society. It is often necessary to accept the 



178 



risks of ch>-(.nicals such as drugs and pasticirV^s when the b.'iiiotits 

warrant their use. Ri^ks impoaed on persons who gain no benefits 

are generally not acceptable. Personal choice, personal values 
obviously must enter into any risk benefit comparison. 

it should be noted that inanKind is already exposed to many 
carcinoqens whose presence in the environment cannot be easily 
controlled. In view of the nature of carcinogenic activity, the 
long latent period of its development, and tho irreversibilitv of 
chemical carcinogenesis, it would be wrong to expose the general 
population to an increased risk if the benefits were small, question- 
able, or restricted to limited segments of the population. 

Tl-se estimation of risk, is based upon p::ny factors included 
in which are exposure, the dose, the animal data, chemical similarity 
and synergistic effects. These many parameters underline the fact 
that when taking into account the safety factor and the uncertainty 
factors involved because of lack of full data, the compleKity of 
assessing the health implications of chemicals, evon when the best 
available means are us.^d, can result in widely varying risk assess- 
ments . 

Through source and supply surveys, followed by source and supply 
analyses by GC/MS combination we can arrive at a measure of supply 
evaluation and from there, m.ake a risk assessment. 

If the risk assessment following the supply evaluation shows 
that some chemical substances are present which should preferably 
be removed from the water supply then a -feasibility study should be 
conducted to determine the most cost effective means of providing a 
high quality water supply. There are a number of alternatives which 
might be considered to provide an adequate water supply. Firstly, 
wo might attempt to find a protected source. Secondly, the eliminat- 
ion of contaminants from the present source should be pursued. Third- 
ly, a possible combination of off-line storage with river supplies 
so that water can be drawn off during periods of good quality. And 
fourthly, treat the water supply to remove the materials of concern. 
As with most problems facing the water industry we must deal with 
existing water plants and their treatment configurjitions and thus the 



179 



third r'.L-ntioned alto rna tiv-^. ir. not feasible in "Tst situations in 
Ontario. Tiieroforo it is with the fourth alternative, the treatment 
of cherpicals of con'-ern, that we have to doal with in most situat- 
ions . 

2. S'iNTHETIC or.c,"iic CirJMICAr.S 

hs outlined previously, the largest portion of synthetic organic 
.c'.'.-^.f.icals found in crinkinq water ar^ thos" forir.od by the reaction 
of orqap.ic precursors with the disinfectant used at the water treat- 
ment plant. In Ontario this disinfectant has traditionally been 
chlorine. Since the discovery (through improved analytical techniques) 
by Rook (10) of trihalomethanes in treated water considerable concern 
regarding their health effects and much experimental attention has 
been directed toward the^e organic chemicals. 

Trihalome thanes 



Trihalomethanos are members of a group of organic chemicals 
that contain one carbon atom, one hydrogen atom, and three halogen 
atoms. The halogen atoms important in the formation of trihalomethanes 
in water are chlorine, bromine and iodine; other halogens are not 
significant . 

In most locations, only A of the ten possible trihalomethanes 
can occur in significant concentrations in chlorinated drinking water. 
However where iodide is naturally present in the water, several 
iodine containing trihalomethanes may also occur. The four trihalo- 
methanes commonly associated with chlorination are as follows (13) : 

Trichloromethane (Chloroform) 
Bromodichloromethane 
Dibromochlorome thane 
Tribromome thane (Bromoform) 

Trihalomethanes are formed by the reaction of free chlorine with 
certain organic compounds in the water. Formation occurs during 
chlorination and can continue to occur as long as free chlorine is 
available . The reacting organic compounds are called ' trihalomethane 



180 



precursor-:^' or just "precursors' . Trihalomethanos are frequently 
called chlorination by-prodacts . The reaction is depicted as ; 

CHLORINE + PRECURSORS > TRIIIALOMETHANES 

(and/or bromine) 
(and/or iodine) 

Precursors are organic compounds, primarily huraic and fulvic 

acid£ pro5ucjd fro:i (Wi-'aving ve^j'statioa; thes-i are f rec:^'3n'^ly 
called natural organics. Synthetic rr.an-made organics are ususally 
not trihalomethane precursors . 

High concentrations of precursors can cause objectionable 
colour in water, can cause taste and odour problems and they can 
act as nutrients for microbiological growth. Precursors are sig- 
nificant because of their role in the formation of trihalomethanes 
and other disinfection by-products. 

Since the natural organic precursors are more commonly found 
in s\irface water, water ta)cen from a surface source is more likely 
than ground water to produce significant trihalomethane levels. 

It will be useful to examine treatment methods to reduce trihalo- 
methanes in finished water since many of the processes proposed 
will apply to other synthetic organic compo\inds also. 

CONTROL OF TRIHALOMETHANES 

There arc three basic ways of controlling trihalomethanes in 
drinking water: 

1) Treatment to reduce the precursor concentration prior 
to chlorination, 

2) Use of a disinfectant that does not generate trihalomethanes 
in water, 

.3) Treatment to reduce the trihalomethane concentration after 
formation. 

These control possibilities will be followed with further details 
being presented of the options available within each of the general 
catrr^nri '. :■ . 



rni 



r.'r.ni? d('-"Ir.iti(j:-0 at ths ^Gr^^:^ u-^-luI wlmn diijcu.r-.sing THM*;; 
are necessary. Theao are: 

l^;-■l1".o.^t:.■^■'-.■■■'ov>^; tr ihal* ■■MioVriane concent raL ions ; this is the 
concentritio!! or trihalomathanes in the water at the moment 
of Hianpllnn. 

terminal trihalome thane concentration; this is the concentrat- 
ion of trihalomethanes that occur when a sample of water is 
jroLc-d fc~ a ji. -.. el": led tii.^e at a ^£)eciiied pH and temi>erature - 

trihalor.itjthane forir-.ation potential; this is the difference 
between the terminal and the instantaneous trihalomethane 
concentrations . 

Because there is no direct measurement for trihalomethane pre- 
curi^ors , the degree of precursor removal must be judged by comparing 
trihalomethane con":entration upon chlorination of an untreated control 
to similar data collected on a treated water after similar chlorinat- 
ipn. 

TRIHAL0;^t::THAN5 PI?^CURFOR REMOVAL 

The first control mode m.entioned above, treatment to reduce 
precursor concentration prior to chlorination, is probably the one 
that has received the most attention. This is primarily due to the 
fact that niodLfication of existing water plant unit operations is 
one of the most feasible alternatives. There are several options: 

a) Move the point of application of chlorine to as late in the 
treatment process as is practical so that most precursors are 
removed prior to chlorination, 

b) If chlorine is applied after coagulation and settling, or after 
settling and filtering, then improve these processes to optimize 
precursor removal. Such things as optimization of pH, poly- 
mer addition and mixing regimes wovild be advantageous in this 
consideration , 

c) Use an adsorbent, either powdered activated carbon, or granular 
activated carbon, for precursor removal prior to chlorination, 



182 



d) Improve ra'V water quality or :-:olect- an alternabe aource of: 
water containlnq less precursor. Again as nent-ioned prev- 
iously, this alternative is generally not a feasible one, 

e) Use a combination of the above, coupled with a reduction in 
cnlorine dose it the reductJ-on can oe acnievea witnouc aaverse- 
ly affecting disinfection. 

Moving the Point of Chlorination 

Chloxiii-i; id applied at water troatraent plants for a number of 
reasons. However, the primary reason for chlorine application diir- 
ing water treatment is for disinfection. The chlorine can be appl- 
ied at various staqes of the water treatment process. Often pre- 
chlorination is used in order to give more time for disinfection through- 
out the plant, and in order to keep bacterial growths and tastes 
and odours and so on, under control during treatment. Post-chlorinat- 
ion is used in order to adjust the chlorine residual prior to dis- 
tribution and in order to achieve the final disinfection step. Mov- 
ing the point of chlorination until after sedimentation for instance, 
would enable the removal of a aignificant portion of precursor mater- 
ial. This of course, places considerable emphasis on the post- 
chlorination step. The maintenance of microbiological quality during 
and following treatment modifications must be ensured. To this end, 
sanitary surveys of the system including biological evaluation of 
the source water are necessary. Additional monitoring to ensure the 
continued maintenance of optimal microbiological quality in finished 
water should be carried out until a steady state condition is reached. 
Also an active disinfectant residual should be demonstrated throughout 
the distribution system at all times during and after any treatment 
changes. 

Coagulation, Sedimentation and Dual Media Filtration 

We have already discussed the movement of the point of chlorination 
within the treatment scheme; the optimization of conventional pre- 
treatment processes can have a significant effect on the levels of 
trihalomethanes formed . 



183 



Ad DO -'pt io n 

rpw dored Activated Carbon (PAC) 

PAC when urjc;i at ^u'tictical doyaqe IcveliJ v/a:3 not found to 
be particularly eff-jctive in renoval of THK precuri-ors. For 
Gxam.plo, at the iinpracticai PAC dose of 100 mg/L one might expect 
up to 50 3 of the prjcursor material to remain after treatment. 

C ranular Activated Carb on (GAC) 

GAC is very effective in reiroving organic material. Tne use 
of GAC for trihalorae thane precursor removal has been studied (8,14). 
In many cases the water supplied to the GAC filter was coagulated 
and se-.tl'^d. *'i-!ve':; '^eloTs o-<hf'U'^tiori -.if '(''■' cnrhun v.-a^.; achievrjd in 
a relatively short time., ie. about 13 weeks for chloroform, 8 weeks 
for bromodichloromethane , 5 weeks for dibromochloromethane and prob- 
ably less than two weeks for bromoform. Tlio possible reason for 
the extremely short breakthrough time of bromoform might be that 
GAC dotiS not rom.ove bro:nide very effectively so that the bromide in 
the effluent plu:; the first breakthrough of precursor will form 
brominated trihalomathanes upon chlorination because the oxidation 
of bromide to bromine by chlorine followed by bromination occurs 
faster than the chlorination reaction. As the GAC ages and m.ore pre- 
cursor breakthrough chloroform will be produced. 

Oxidation 

Most work in this area has been carried out on three oxidants 
namely: ozone, chlorine dioxide and potassium permanganate. 

Ozone when used at practical dosage levels has been found to 
be not particularly effective for removing trihalomethane precursors. 
Data compiled by Trussell et al (15) from independent work of several 
investigators showed that ozone precursor removal ranged from negative 
removal to up to 90% precursor removal. Tliere are several variables 
which can account for the wide range of results: firstly of course 
the nat\ire of the precursor, in addition the ozone dose , contact time , 
contact design and the dispersion system together with other water 
quality factors. Th.e use of chlorine dioxide has shown some removal 



184 



of precursor rEi;Vfea:^ial following the application ol' clilorine diox- 
ide Clft). The chlorine dioxide has some effect on the precursor 
such that it is changed so that it will not react with subsequent 
chlorine to form trihalomethanes . Precursor alLe ration/removals 
of up to S0% have be»^n obtained when chlorine dioxide is applied 
in the disinfection dosage range of between 1 and 2 ppm. Ejcpori- 
monts with potassium permanganate as a pre-oxidant have shown 
relatively sinali percent removals of precursor (17). Precursor 
removals as measured by potential trihaioiaechane f^rinatioa have 
achieved maximum levels of only up to 20%. Again, it is thought 
that raw water quality and hence the kind of precursor material 
present will affect this process. 

Table 1 (page 11) gives some indication of the effectiveness of 
various unit processes for reducing chloroform formation potential. 

Aeration 



In general aeration has not been found effective for reducing 
trihalome thane precursor materials from raw water at economical air 
to water ratios. 

Biological Processes 

The use of biological processes to break down organic chemicals 
has been given the renewed impetus in recent years. Riverbank filtrat- 
ion and slow saind filtration have been in use for many years and the 
quality of treated water has been high. Even at rates well above 

those usual for slow sand filtration, for example, up to 3 or 4 gal/ 

2 
min/ft biological filtration has been successful an removing organxcs. 

More recently, in Europe, ozonation followed by activated carbon 

filtration )ias become a widely employed step in the water treatment 

process. This process commonly known as biological activated carbon 

or BAG has demonstrated that it can play an important role in the 

reduction of surrogates such as dissolved organic carbon and, to some 

extent, total organic chlorine. 



TABLE 1 



EFFECTIVENESS OF VARIOUS UNIT PROCESSES FOR REL'UCIKG CIILOROFCRM 
FORMATION POTENTIAL (11) 



Process 



Chloroform Formation 
Potentialytig/L 



Aeration followed by 
chlorination 



Coagulation , Sedimentation 
and Dual-Media Filtration 
followed by Cnlorination 

Coagulation, Sedimentation, 

Filtration/Adsorption by 
Granular Activated Carbon 
(5 m.in. contact time] follow- 
ed by chlorination 

Powdered 7\ctivated Carbon 
added after Coagulation & 
Settling followed by 
chlorination 

Ozone only 



Ozone followed by chlorination 
Chlorine Dioxide only 



66 



48 



43 



27 



48 

4R 
74 



Chloroform 

Formed 
/Ag/L 



66 



13 

Si 
<10 

§ 
None found 

43 
<1 



Remar'!<.s 



Diffused-air aerat: on -rith 
air to water ratios up to 
20:1 did not reduce ch-^oroform 
formation potential (10 min. 
contact tif..-) 



GAC would b? effective for 3 wks. 
GAC would b:- effective for 8 v;ks . 

at PAC dosage - 8 r.y/L- 

at PAC dosaq? - 100 s.q/L 
PAC contact l-.im.e = 2-2(' min. 

O3 neither forms trihalometlianes , 
nor removes precursors at disin- 
fection doses 

Disinfection doses {<,l mg/L) 

CIO2 does not form THM 






Process 



Chloroform Formation Chloroform 
Potential Ajq/L Formed 



RerrarJcs 



Coagulation, Sedimentation S 
Dual Media Filtration followed 
by: 

1) Chlorination 

2) Chlorine dioxide with 
chlorine 



17^ 



1.3 mg/L CIO2 and 1.5 mq/L CI2 

THM formatioh decreases as the 
ratio of CIO;, to CI2 increases 



All tests perforir.cd on Ohio River water. Chloroform Formation Potential is the 
amount of chloroform formed when raw water is chlorinated past break-point and 

stored at 25° C for a specified contact time. 



a - chlorine contact time = 48 hours 
b - chlorine contact time = 9G hours 
c - chlorine contact time = 22 hours 
d - contact time for combination of chlorine 
dioxide with chlorine = 22 hours 



00 



xm 



Th-j bc-nofitfj of, as well a^ the problerns associated with, 
chanqi-v: to som^-'. alternative method of disinfectant must he weighed. 
For example, ozonation, while not creating chloroform, also does 
not provxde any residual disinfectant in the distribution system. 

Since ifany of the alternative disinfectants or their corresponding 
by-producfca may have some undesirable properties* the first principle 
ohoui; be 'o ap;>L'-' v'h-itev^ ■: trej.^.Te-it is nOr-^(V:d to provide water 
of high quality and low organic chemical content prior to the applicat- 
ion of a disinfectant. in this way the chemical disinfectant demand 
of the v/ater would be minimized and pathogen control will be maintain- 
ed while disiuLOctant u=ic and by-product formation will be minim.ized. 
At the present time a Provincial Lottery Funded programme is being 
carried out to study ozone as an alternate disinfectant, when used 
alon-s or in combination with chlorine, and to study in particular the 
by-products of ozone and examine their health related effects when 
in finished drinking water. Mternate disinfectants of course, include 
such oxidants as ozon-^ , chlorine free chlorine dioxide, chloramines 
and to a lesser degree potassium permanganate. Ultraviolet disinfect- 
ion has also been considered. It is important to reiterate that in 
all cases, residual disinfectant needs to be maintained throughout the 
distribution system. 

Chlorine Dioxide 



Chlorine dioxide may be a promising alternative to chlorine be- 
cause a disinfectant residual can be maintained in a distribution 
system. This residual is reportedly comparable to chlorine as a bio- 
cide and, if the concentration of excess chlorine use to generate 
the chlorine dioxide can be kept low, the trihalomethane concentrat- 
ions in the finished water will also be low. 

There is some question concerning the health effects of ingesting 
chlorite iron. Chlorite converts hemoglobin to methemoglobin, and 
some health authorities have recommended the absence of chlorite 
in drinking water. Low dosages of chlorine dioxide of course have 
been used in the past for taste and odour problem eradication. 



188 



I..::: jr.u 



Ozone is another effective disinfectant that does not produce 
trihalotnethanes but it fails to provide a residual disinfectant in 

the distribution system and, like the other alternatives to chlorine, 
little is known about its or^rranic by-products. 

Cnloramines (Chlorine dIus Axmnonia) 



The use of a chlorine residual in a less active form such as 
chlorine TOicisir-e-l with, aav.ior.ia (chloraraipo or combin^^d c!"'.iorinj) 
will significantly reduce trihalomethane formation. 

Combined chlorine is not as reactive as free chlorine for the 
formation of chloroform. Therefore if a utility adds ammon^' "i in con- 
junction with chlorine addition or shortly thereafter, such that 
no free chlorine residual existed for long, while still being compat- 
ible with good disinfection, trihalomethane formation shoiad be low. 

Since chloramines are less active than free chlorine, chlormaines 
are much less potent disinfectants than free chlorine. In fact, early 
studies, subsequently confirmed, demonstrated that chloramines requir- 
ed approximately a 100 fold increase in contact time to inactivate 
coliform bacteria and enteric pathogens as compared to free available 
chlorine (18). For this reason, chloramin;?s are not recommended for 
use as primary disinfectants in drinking water treatment. Chloramine 
treatment finds its widest apjAication in the maintenance of chlorine 
residuals in distribution systems, after the primary disinfection 
with free available chlorine or other disinfectants. 

The microbiological quality of the finished product is still the 
foremost considerated in drinking water treatment. Use of alternate 
disinfectants, therefore, must be an effective barrier against problem 
organisms while still bearing in mind the health effects of possible 
by-products. 

TRIHAIOrjlTHANE REMOVAL (after formation) 

Trihalomethane removal can be achieved by granular activated carbon, 
however tho bed life and consequent bod replacement is so low as to 
make the x-^rocesG non-viable in most cases. 



189 



.-C'::!!-:^ ha.vo ;:j:'r. con iv.ctud on reino /inq alrt-iaJ/ formed L.L'ihalo- 
rr.ethanjs from drinking v:ater by the use of PAC adsorption, ozonat- 
ion, and treatr:'.ent with chlorine dioxide. The.-^e processes were 
shown ho be not oarhicularly effective at removing trihaloroe thanes 
from the vrater- 

V/ith rCjc^-d to the aeration treatment process it ha::5 bean shcvn 
that particularly in the case of chloroform, which is volatile, 
the material will bo lost from the water at any air/water interface. 

Table 2 gives an indication of the effectiveness of various 
unit processes for the removal of chloroform from drinking v;ater. As 
can be seen the aeration process appears the most viable of those 
indicated in terms of an on-going practical methodology. 

TABLE" 2 



EFFECTIVrENESS O? V?.RIOUS XJHIT PROCESSES FOR 
REDUCING CHLOROFORM TH DRINKING 
WATER (11) 



Process 



Initial Chloroform 
Concentrations ,yH cj/h 



50% 



25% 



10% 



Aeration 

Air to Water Ratios 
for diffused-air 
aeration: 10 min. 
contact tim.e 

Granular Activated Carbon 

Expected life for 5 min. 
contact time 

Powdered Activated Carbon 

Dosage, mg/L applied to: 

a) Chlorinated Raw Water 

b) Chlorinated, Coagulated 
and Stjttled Water 

Ozonation 



100 



■is 

€.4 
44 



6:1 



7 weeks 



15 :1 



25:1 



5 weeks 4 w6eks 



95 mg/L > 105 mg/L > 105 mg/L 
27 mg/L 90 mg/L 105 mg/L 



4 min . contact time 

q-ilorino Dioxide 

Up to 48 hr. contact 
time 



Up to 25 mg/L O3 had no effect 
on the chloroform concentration. 



Up to 10 mg/L CIO2 had no effect 
on the chloroform concentration. 



190 



Sya thetic O r ganic, Che!r.ic ::;ls - Inc:u3<-.rl al (Man-Mado) 

We have discussoj th*^ or^janics v;>'ifh might be prosent in v/ater 
supplies, namely: naturally occurring organic substances such as 
humic and fulvic compoiLnds; those organic chemicals, such as trihalo- 
methanes, formed during water treatment and the final organics to 
be exaniincd r.re thoce rr-an-madG synthiatic organic chemicals 
present in a water supply. Thesa include such coi?poiind'.i as pesticid- 
es and other organic constituents such as benzene, benzopyrene , 
carbon disulphide, carbon tetrachloride, pentachlorophenol, poly- 
chiorinatod biphenyls, vinyl chloride which are industrially originat- 
ed chemical compounds. Generally, majiy of the same unit processes 
as applied to trihalomethane and trihalomethane precursor removal 
apply in the case of the synthetic organic chemicals. A summary of 
the presently available treatment processes as outlined by Trussell 
and Trussell (9) is: 

Aeration 

diffused air 

packed towers 
Coagulation 

Al 111 

Fe 111 

polymers 
Oxidation 

ozone 

chlorina dioxide 

permanganate 
Biological Processes 

riverbank. treatment 

biological active carbon 
Adsorption 

powdered activated carbon 

granular activated carbon 

synthetic organic carbon 

It will be worthwhile to look at these treatment modes and their 
application to drinking water treatment in more detail. 

Aeration 

Aeration as a unit process for removal of organics has been in- 
adeqi^ately evaluated to date. Work by McCarty et al (19) and by 
Singley et al (20) have demonstrated that air stripping can be effect- 
ively used to remove a variety of snythetic organic chemicals of a 
volatile nature. The efficiency and the material removed will 



191 



abv-:o-., -i'- d'^fir-'' '■/.'-.■■•v. t>..r. ch>r.icA' qn?.l.lty or the 'v.-it^r to h:-. tr-^ist- 
cd. It i:-i iir.oortarit to note hnre that the significance of utar.o rials 
released to th2 atrrioaphere follQ.ving air stripping needs further 
study. 

Coacyulatiop. 



Coaqulation with rietal nalts has betm used in drinking water 
treatment for many years. Coagulation is effective in removing 
many trace contaminants and is the main method for removal of colour 
in riortii jVn:-;ri-ja. i:t it; an o f'ilciunf. nean:5 of roiTioving aquatic 
organ i.cs of a hitiiic origin during treatment thereby reducing the sub- 
sequent formation ol trihaloniethanes , however , little work has been 
done to evaluate thn effectiveness of coagulation in the removal of 
the many synthetic organics of concern today . It is feasible that 
the coagulation process will be effective in removing high molecular 
weight organics especially those adsorbed on particulates but the 
removal of volatile organics would seem a more difficult proposition. 
As with many of the unit proccntjes indicated the use of coagulation 
in combination with other processes might be needed to achieve specif- 
ic results. Certainly coagulation can be optimized to achieve maximum 
organic carbon removal for each particular raw water quality. 

Oxidation 



Tlic oxidation of synthetic organics through chlorination is clear- 
ly under considerable scrutiny today. The possibility of further 
chlorinated organics is a situation which is to be avoided. Examinat- 
ion of the effectiveness of the other three most common oxidants 
mentioned previously, that is, ozone, chlorine dioxide and potassium 
permanganate suggests that although each of these is somewhat effect- 
ive with certain compounds, or with most compounds under the correct 
conditions, none of them seem applicable in the broad scope of drinking 
water treatment. In addition, again it must be borne in mind that 
by-products from these alternate disinfectants must receive detailed 
investigation before their general acceptability for use as a process 
alternative . 



192 



Biological Processes 

The use of these procc.-:.ses has been outlined proviously and 
is currently receiving close attention world-wide. This continued 
examination of such a treatment is necessary to ascertain the 
effectiveness in removal of the broad range of synthetic organics 
found in raw water supplies. 

A d-io'-'pt Lor. 

In terras of adsorption is has traditionally been the case in 
North America to employ PAC to remove trace organics especially those 
associated with taste and odour compounds. Recent evidence has 
shown that PAC is not a particularly broad spectrum process and is 
effective at removing only a small number of higher molecular weight 
componnds. In th? same way synthetic organic resins have recently 
been evaluated; some of these have demonstrated effective removal 
of humic substances, some will remove low molecular weights synthetic 
organics, and others are particularly effective in trihalome thane 
removal. Many of these resins can be regenerated in-situ with steam, 
however, their high capital cost of selective removal characteristics 
make them border-line feasibility for use alone. Use in combination 
with other treatment unit operations can be effective. 

Granular Activated Carbon (GAC) is presently the only unit proc- 
ess available that has a proven ability to remove a wide range of 
organic chemicals from aqueous solution, rne mode of use of GAC will 
depend greatly on the type of organic chemical which is wished to 
be removed from solution. GAC can be used as replacement for the 
coal into the media filter or GAC contactors can be built as addition- 
al units to the conventional treatment processes. 

GAC can be used most effectively in the number of treatment 
combinations; these were outlined by Trussell and Trussell (9) in 
the following diagram. 

Om:-! again, of fcctivf-mn;:; of each oF the^e alt.crnative;; would 
depend greatly on the- type of organic material to be removed from 
water and various other process variables. 



k=^^ :'odoi5 of Procoss Operaticn 



193 



c "' '': 



^ 



~^ 



DZ 



*_ 



Thermal 
r'egGnp.ration 



A. Conventional GAC 



Ozonation 



GAC 



Roplaceinent 



. Ozone-Enhanced Biologically Active Carbon 





Ion EKC^-anqe 
RGsin 


*- 


GAC 


s 


*' 


• 






t 




? 






Staam 
Regeneration 


■ 1 

Replacement 



f^ 



C. Synthetic Resin Pretreatmcnt 

r Replacement 



Enhanced 
Coagulation 



H Sedimentation 
Filtration 



-5> 



GAC 



Steam 
Regeneration 



n. Enhanced Coagulation and Steam Regeneration 



"enhanced 
Coagulation 



Sodinontation 
Filtration 



"^ 



Air Stripping 




Replacement 



E. Enhanced Coagulation, Air Stripping Conventional GAC 



■5* 



PAC Adsorption 



Sedimentation 
Filtration 




I.. -■:". £rb\f^rpi;-LOi-i, Air stripping 



19A 



bench-scale, pilo--~.^cale and field-scaie pilot studies in order to 
better define their effectiveness and refine estimates of the capit- 
al and op&rational .-O-sts. 

SUMMARY 

This brief overview of organic contaminant removal in drinking 
water has looked at the two major classes of organic chemical con- 
tamin,,?.r\"Cs In diiii^icirii^- "W:itii*. "Ip.e^e arc; those of natural origin 
and those of synthetic origin. The synthetic chemicals were sub- 
divided further into two groups. The first group, those chemicals 
that result from water treatment practices, and the second group, 
those synthetic organic chemicals resulting from our wide-spread 
use and manufacturer of synthetic organic chemicals. These chemicals 
have been, and are likely to continue to be, contaminants in our 
sources of drinking water and as such constitute some risk to the 
health of the consurer. We can obtain an estimate of the risk for 
many of the chemicals, whilst for many we have insufficient data to 
be able to estimate even at any very conservative extrapolation 
procedTire, and thus wa must continue to study these chemicals. 

Treatment niethods were outlined to deal with those organic com- 
pounds of concern identified through a source survey and analysis. 
The process alternatives can be used alone or in combination with 
other unit processes in order to achieve the reduction of the 
particular organic chemicals. It is important to investigate the 
processes available, for different water qualities, by means of 
bench-scale, pilot-scale and rl^"int-scale studies. Only through such 
studies wo will be .ible to determine which processes are applicable 
to certain waters and which processes offer a broad spectrum of 
treatment for the removal of organic chemicals from our drinking 
water. 

Scientists have been charged with irresponsibility for commenting 
with alarmist-type reports prior to a full study of highly technical 
work and its long term public impact. It is therefore important 
that time is taken to investigate both the concerns and the treatment 
optionn thoroughly. In this v.-ay it should be posr^ible to arrive at 



195 



a tK(ji.v?r anti tea.; -T'.'-hi,' a;3sc:;-."ir.u;iil. or t\\v sii.uat \.o^\•, thiiu ii'.'pi.-- 
fully v.'ill bG the optimam solution. 

In m.any caoc^^ v;e do not have the tools to aniiv/er the fears 
of con^i-uners nearly as quickly as we would wish and some way of 
communicating the r.eed i:or time to anower the questions must be 
found. Responsible reporting would further this need, and in addit- 
ion, the credibility of scientists and those in positions of 
authority, which has been sorely strained in recent years would be 
enhanced. rnus it must be stressed that in the long term it is 
probable that the most reasonable solutions both from a practical 
and economic view-point will be obtained if the problem is investigat- 
ed in a logical manner. 



196 



?t:v..'.'' .:-.^?:iY 

I. tlicholson, .".A. et al; "Organics ir. Ontario Drinking V/atcr, 

Part ir, Ontario ministry of the Environment, (April, 
1977) . 

2- Symons, J.M.; Bellar, T.A.; Carsuell, J.K.; Demarco, J. ; 

Xropp, I'.L. ; Kobeck, G.G . ; rseegcr , D.R. ; t>locviin, CJ.-, 
Smith,, B.L., and Stevens, A.A. , "National Orqanics 
Reconnaisance Survey for Halogenated Oryanics", JAVJWA, 
67: 634, (1975). 

3. >KtWn.-il 0r.-:anic3 ^'"oni "-orlng Curvoy (N0M3) . T.-^chn.i nal I'^upport 

Division, Office of Drinking Water, US EPA {197S) . 

4. Page, T. ; Harris, R.H., and Epstein, S.S., "Drinking Water 

and Cancer Mortality in Louisiana", Science, 193:55, (1976). 

5. Guidelines for Canadian Drinking Water Duality, 1978; Health 

and Welfare Canada (1979) . 

6... U.S. Federal Register, 43: No. 28, 5756-5780, (Feb. 9, 1978). 

7. Tardiff, R.G., "Health Effects of Organics: Risk and Hazard 

Assessment of Ingested Chloroform", JAWWA, 69: 12, 653 
(Dec. 1977). 

8. Symons, J.M., "Utilization of Various Water Treatment Unit 

Processes and Treatment Modification for Trihalomethane 
Control", Proc. Control of Organic Chemical Contaminants 
in Drinking Water. Seminars sponsored by The Office of 

^ Drinking Water, U.S. EPA, Jan, 1980. 

9. Trussell, R,R. , and Trussell, A.R., "Evaluation and Treatment 

of Synthetic Organics in Drinking Water Supplies". JAWJA, 
72:458 (Aug. 1980) . 

10. Rook, J.J., "Production of Potable Water from a Highly Polluted 

River", Water Treatment and Examination, 21: pt. 3, 
259 (1972). 

II. "Drinking Water Detoxification", Bk . Ed., Gillies, M.T., Koyes 

Data Corporation, Park Ridge, New Jersey, U.S.A. 1978. 

12. "Drinking VJater and Health", pub. ^:ational Academy of Sciences, 

Washington, D.C. June, 1971^ 

13. Bellar, T.A.; Lichtenberg, J.J., and Kroner, R-C. "The Occurrence 

of Organohalides in Oilorinatod Water", JAWWA, 66:12:703 
(Dec. 1974) . 

14. Symons, J.M., "Sumn^.ary of Granular Activated Carbon Practise Data", 

Water Sup.ply Research Division U.S. EPA, Cincinnati, Ohio, 
(Feb. 17, 1976) . 



197 



15. Trujs^ll, P.R., and Umphrea, M.D., "The Formabion of Trihalo- 

ncthancs", JAWWAVO: 11: 604 (Nov. 1978). 

16. Symons , J.M., and Stevens, A.A. , "PhvGical-Chemical Treatment 

for the Removal of Precursors", Conference; Karlsruhe, 
Germany, (Sept. 1978). 

17. r^anq, M.C., "Reduction of Haloforrrj ip Drinking Water Supplies", 

Ontario Ministry of the Environment Research Report, fr69, 
(Sept. 1978) . 

IS. ■Eut'iGrfitJlJ, C.T., and Viat*:lti, '£ . , "Polative Resi'jtanco of E. 
coli and E. typhosa. to Chlorine and Choramines", Pub. 
Health Reports, 59, 1661 (1944),. 

19. McCarty, P; Reinhardt, M. , and Argo, D. , "Organics Removal 

from Advanced Wastewater Treatment", Proc. 97th A^VWA 
Annual Conference , Anaheim, California, (1977) . 

20. Singley, J.E.; Ervin , A.L.; tiangone, H.A.; Allan, J.H, , and 

Land, H.H., "Trace Organics Removal by Air Stripping", 
A^v^'^A Research Foundation Report, May, 1980. 



198 



ORGANIC CONTAMINANT REMOVAL 
IN DRINKING WATER - FIELD EXPERIENCES 



By: 
R.B. Hunsinger 



Ministry of the Environment , 
Province of Ontario, 

Technology Transfer Conference, No. 1, 
Tuesday, November 25, 1980. 
Skyline Hotel - Toronto 



m 



Dealing with micro-contaminants in drinking water involves 
four basic steps: 

1) Risk Assessment - To ascertain if the contaminant represents 
a problem and how much hazard is involved, 

2) Analysis Methods - To insure precise and accurate measure- 
ments of the contaminant in question, 

3) Survey - To determine the source and extent of the contaminat- 
ion, 

4) Removal Methods - To reduce or eliminate the contaminant if 
necessary. (1,2). 

These four processes should theoretically be carried out in 
the order given, although in practice risk assessment is often 
not complete or even adequately begun, before it is necessary to 
move on a problem and explore the ramifications of a micro-contaminant 
in terms of analysis, survey and removal methods. Step one, risk 
assessment may be temporarily by-passed but the second phase of 
analysis methods is a pre-requisite step to proceeding to a survey 
or ciny study of removal methods. 

Assessment of analytical methods is a most difficult problem 
for the water treatment engineer. Most of the chemistry involved 
is highly technical, experimental in nature, and has not been around 
for sufficient time to be examined even by the analytical scientific 
community. The first criteria in dealing with contaminants is to 
ascertain that accurate and precise measurement is possible. To 
cite an example of the type of problem that can emerge: In Ontario 
Asbestos Studies, the data gathered in 1972 for asbestos in water 
caused alarm with reported levels as high as 25-40 million fibres/ 
litre. The only valid statement that can be made today regarding 
these figures is that there was fibrous material in the samples. 
Qualification, let alone quantification is not possible. 

One method which has been used with some success in terms of 
method selection is the setting up of a committee of experts to 



200 



examine the various methods available and reach some consensus 
as to the most viable method and how the various methods compare. 
This is not a quick process but a sound analytical base is essent- 
ial prior to any detailed problem investigation. The committee 
ideally should include analysts from industry, government and 
universities and it should be the aim of such a committee to com- 
pare various methods available by experimental means and inter- 
laboratory comparisons and in the end to reach some general agreement 
as to which method to recommend as a standard. The publication of 
such a method also affords those analysts who might object, the 
opportunity to formally disagree and possibly open further dialogue . 
The committee should also have an on-going function of analytical 
method revisions as new information comes to light. Very few 
methods stay static for any amount of time but the changes should 
be carried out in a unified industry-wide manner. 

It can not be strongly enough stressed that we must have a 
tellable standardized method of measurement for any new or exotic 
contaminant in water as a first step to any program of monitoring 
or research on removal. Further, method development must be a 
separate and primary fxinction and not part of surveys of drinking 
water. The water that our customers consume is much too important 
and emotional an issue to give out information based on half-baked 
ideas or hypothesis. 

Examination of methods of analysis for trihalomethanes (THM) 
would show that the Purge £ Trap method (3) as developed by the EPA 
is becoming the industry standard and is the method of analysis 
on which most trihalome thane regulations are based including the 
Guidelines for Canadian Drinking Water Quality (4 ) as well as the 
about to be published, Ontario Drinking Water Objectives (5 ). 

Chloroform represents approximately 90% of the THM's found in 
water and as the reaction for the other trihalomethanes is similar 
in form, but varies quantitatively we shall deal with chloroform only 
in the discussion of methods of analysis. The Purge s Trap measures 
the purgeablc or free chloroform. 



201 



The MOE laboratories have the capability to do the Purge 
& Trap method but prefer and routinely use the Direct Aqueous 
Injection Method or DAI method for THM which is a method develop- 
ed by Meresz & Nicholson of the MOE (6,7). The DAI has the 
advantage of being much less expensive and a faster form of analysis, 
The DAI method produces chloroform results that are 1.5 to 2.2 
times as high as those produced by the Purge & Trap method and 
thus overestimates the amount of free chloroform present. The 
explanation for this is that chlorination of natural waters causes 
the formation of certain non-purgeable intermediates that decompose 
within the gas chromatograph injection port to produce additional 
chloroform. Hence, the DAI is measuring not only the purgeable 
free chloroform but also a certain portion of the non-purgeable 
intermediates which have been converted to chloroform in the 
analysis process. The amount of intermediates converted to chloro- 
form is site specific, but a fairly consistent DAI/free chloroform 
ratio can be developed. m the Belleville study, the ratio was 
determined to be 1.9/1. The conversion of intermediates is also 
a function of the design of the gas chromatograph used (8,9). 

The DAI always produces numbers that are an overestimation of 
the free THM and thus is an excellent survey analytical method 
as it readily flags the areas of concern and has the advantages of 
being inexpensive and fast and thus allows survey programs that 
are more extensive than would be allowed by the Purge S, Trap given 
the seime monetary input. 

When a survey location is flagged as approaching the limit 
for trihalomethanes, Purge & Trap analysis can commence to insure 
compliance with the limit. Many locations in Ontario have DAI 
levels in the range of 10 yg/L which would translate to 7.5 yg/L, 
free trihalomethanes (10) and it is a waste to use an e3^)ensive, 
accurate, analytical tool to insure complicince with a limit of 
350 pg/L. Further, the numbers produced by the DAI are comparable 
over the long term for any given site . 



i-M'' 



202 



There have been about 700 organics identified in drinking 
water with the use of gas chromatograph-mass spectroscopy (GC/MS) 
and more are being added frequently. 

When the Brantford Project was begun in 1978, an attempt 
was made to develop an organic scan using a GC/MS in which a 
graphical presentation of the organics present in the water albeit 
in an unidentified and unquantified form^v^ould be available. In 
this manner it would be possible to compare general organic 
removal across a process and possibly identify and quantify 
substances of interest. This work was attempted based on the 
findings of Grob & Grob (11). Although the method was tested 
extensively by a contractor at the University of Western Ontario, 
it was found to be too cumbersome given the present state-of-the- 
art and the project was finally abandoned. A current Research 
Advisory Committee project is investigating this further. 

As noted above, specific organic measurements are expensive, 
difficult and sometimes not even possible, so the use of surrogate 
organic measurements has become a much sought after panacea- Surrog- 
ates include such things as: 

TOG - Total Organic Carbon 

DOC - Dissolved Organic Carbon 

TOX - Total organic Halogen 

TOCl - Total organic chlorine 

UV - Ultraviolet (Extinction @ 254) 

TOC is the most common organic surrogate seen in the literatiire. 
MCE uses a DOC which is similar to the TOC but does not measure 
the particulates. 

These surrogates are extremely useful measurements but are 
analytical method specific and vary greatly from laboratory to laborat- 
ory and thus in many cases, are not directly comparable and are in need 
of standardization. 



AS mentioned above, a survey may begin before risk has been 
thoroughly assessed but analytical method development must be a 
prerequisite to any further work. This was in fact the case for 
trihalomethanes in that the DAI method was in place at the 
survey commencement. The risk assessment for THM has been much 
harder to come by, in that approximately 6 years after the commence- 
ment of the survey, we are about to have published for Ontario, 
a THM limit of 350 ^g/L. This limit is based on the same risk 
information on which EPA derived their limit of 100 \ig/h. Both 
limits refer to free or purgeable THM but the U.S. limit is 
based on averages over time whereas the Ontario limit is based on 
a single occurrence exceeding the limit. 

A survey for the purpose of monitoring THM in Ontario was 
initiated in 1974 with 29 municipalities and has gradually been 
increased to the point that in 1980, there are 132 municipalities 
being monitored. 

The general rationale behind the selection of the municipalities 
to be monitored first was a combination of probable occurrences based 
on humic content of the surface water, population size and also 
representative samples from the various watersheds. 

The most up-to-date results of the survey for chloroform in 
Ontario are presented in Table 1 (10). 



TABtE 1 



DAI CHLOROFORM LEVELS IN ONTARIO DRINKING 
WATER SURVEY 1980 

Chloroform Level Number of Locations 

- 100 yg/L ^2 (57%) 

100 - 200 " 25 (23%) 

200 - 300 " 13 (12%) 

300 - 400 » 6 t^*' 

400 - up ■> 2 (2%) 



204 



As can be seen, about 80% of the locations have chloroform 
below 200 Ug/L. Considering that chloroform represents 90% 
of total THM and also that the DAI is measuring about 1.5 - 2.2 
times the Purge & Trap, then 80% of the locations in Ontario 
presently being monitored, (which are considered to be the 
locations with the highest probability of THM occurrence) are 
below 100-150 Ug/L frf>e THM. Eighty percent of the locations 
examined have THM maximums below 50% of the proposed limit. 

Of the remaining 20% of the locations those approaching the 
limit would be switched to a monitoring program based on Purge & 
Trap to better assess the situation or at the least a Purge & 
Trap-DAI comparison would be done in order to establish a ratio. 

After the establishment of this more accurate monitoring, 
the next step woxild then be to attempt to identify the cause of 
the high THM levels, and lastly determine suitable design and 
operating measures for reducing these siibstances, while ensuring 
that adequate disinfection is maintained. 

In terms of removal methods, an extensive in-house MOE program 
on removal was carried out. Fvirther, the Research Advisory 
Committee has sponsored two organic removal projects; one in Belle- 
ville and one in Brantford. Complete descriptions of the activit- 
ies of these programs are beyond the scope of this paper, but 
specific areas from each are described below in order to illustrate 
the nature of the field experiences with the removal of organic 
contaminants . 

Bench-scale studies at MOE by Fung (12) were begun in the mid 
70's to determine the effectiveness of reducing the chloroform 
precursors prior to their conversion to chloroform. This process 
assumes the use of post-chlorination. This study examined 
effectiveness of: 

1) coagulation utilizing various types of coagulants and coagulant 
aids, 



205 



2) adsorption on granular activated carbon (GAC) , 

3) the use of powdered activated carbon (PAC) . 

Results of the research studies on the reduction of pre- 
cursors shows that : - 

1) substitution of post-chlorination for pre-chlorination 
generally decreased the amount of haloform in the effluent 
by 50% in any given process configuration, 

2) Using post-chlorination, the efficiency of alum used alone 
was about 44%. With the addition of activated silica, 
the efficiency was increased to about 90%, 

3) Reduction of haloform precursors was not significant when 
using PAC at a generally accepted rate, 

4) GAC was found to be effective in reducing haloform precursors 
up to 90% regardless of the pre -treatment processes, 

5) Ozone, potassium permanganate and hydrogen peroxide were 
tested as possible alternate oxidants to chlorine in the pre- 
treatment processes and did not affect the performance of 
the subsequent coagulation in reducing chloroform precursors. 

The Belleville project funded by the Provincial lottery was 
carried out by the Belleville P.U.C. and Gore & Storrie Consulting 
Engineers (13). This was a full-scale project designed to ascertain 
the effects of moving the chlorination from one end of the process 
to the other. No alternate method of disinfection was being used 
at the head of the process. 

The primary objective was to determine what effect this dis- 
continuation of pre-chlorination would have on the following: 

I) the removal of precursor organic compounds and the resultant 
change in THM levels with chlorination applied after the 
coagulation, settling and filtration processes. 



206 



II) The quality of the finished water in terms of parameters 
such as taste and odour, turbidity and colour, 

III) Plant operations and water production. 

The problems anticipated as a result of the disconLinuation 
of pre-chlorination were: 

I) possible taste and odour increase to processed water in 

the settling tanks imparted by unchlorinated settled material, 

II) possible biological growths in the filters resulting in 
shorter filter runs and degraded filtered water quality. 

The plant was split for this project with a small portion of 
the flow going through coagulation, f locculation, sedimentation 
and filtration and then on to post-chlorination. The post- 
chlorinated water was sent to waste due to the experimental 
nature of the treatment . 

In terms of objective TI, namely the effect on other parameters 
such as taste and odour, colour, turbidity, etc., the average values 
for the specific parameters as well as a percent reduction through 
the process for the 9 month period from February to October cover- 
ing both cold and warm water conditions show very little difference 
between the pre-chlorinated and post-chlorinated streams for 
turbidity, colour* taste and odour. 

Similarly, the altered water quality going onto the filters 
did not negatively effect the headloss. In fact, a slight improve- 
ment was noted in the post-chlorination stream. Physical examinat- 
ion of the filter media and filter walls showed no biological growths 
or other unusxoal accumulation of material. 

Comparison of the results obtained for the two methods of 
plant operation, experimental (post-chlorination) and normal (pre- 
chlorination) , shows virtually no difference in the levels of 
chloroform and THM's present in both settled and filtered water 
samples. During the February to October time span, the average values 



207 



for chloroform in water after filtration were 104 lig/L (f>ost- 
chlorination) and 102 pg/L (pre-chlorination) . Both methods 
did achieve some improvement in chloroform and THM levels as 
compared with chlorinated raw water samples, indicating that 
the coagulation and settling process does remove some precurs- 
ors and THM. 

The average reduction in TliMs across the flocculation and 
settling phases of the plant process were between 13% and 15%. 

Work reported by Love et al (14) and Fung (12) in the MOE 
bench scale studies suggests an expected reduction in trihalomethanes 
in the range of 50% due to the moving of the chlorination point. 
This was not the case in the Belleville water. This is becoming a 
recurring theme when dealing with organic removal. The broad spectrum 
solution does not seem to be applicable, rather, we find ourselves 
having to examine many possible processes in each specific case. 

R.A.G. Simmons (15) reported to AWWA in 1980 on further work 
carried out at Belleville under Lottery Funding. The bench-scale 
work consisted of chlorinating the raw water for a given time to 
achieve a given level of disinfection (500 colonies/100 ml total 
bacteria count) . Following the achievement of this level of 
disinfection, the water was then chemically dechlorinated to 
and then rechlorinated to 0.75 and 1.5 mg/L, Simmons states that 
a chlorine dosage of 4.5 mg/L for a contact time of 25 minutes, 
necessary to achieve the 500 colonies/100 ml bacteria criteria, 
then dechlorinated/rechlorinated to 0.75 and 1.5 mg/L produced 
142 pg/L & 205 pg/L of chloroform respectively after 24-hours 
contact time. A similar dosage of 4.5 allowed to stand in a 
control sample for 24 hours produced 275 yg/L chloroform. The 
paper goes on to develop the senenario to include costs and operat- 
ional variables. Although dramatic, the results are based on 
limited bench-scale experiments; future research may look at this 
scheme further. 

Ihe Brantford project is a pilot plant operation; the main purpose 
of which is to test the effect of GAC on the removal of THM precursors and 



208 



other organic ccroipounds from the water prior to chlorination. 
This project goes one stage further than the Belleville experiments 
in that it is not only testing post-chlorination but is also 
going to determine the effects on chlorinated organics of 
substituting GAC for the anthracite in the present filter beds. 
As with any other maidification the status quo must be maintained 
in terms of other treatment parameters. For example. Brant ford 
is now using PAC for taste cind odour removal and thus the GAC 
must be able to maintain the taste and odour control as well as 
remove the organic precursors. Further, the adequacy of disin- 
fection must be maintained. The Brantford project is also being 
funded under the Provincial Lottery system and is being operated 
by the City of Brantford Public Utilities Commission under the 
direction of K. Edwards. 

Fundamental information in regards to the behaviour of the 
organic contaminants is often not fully developed and hence much 
time is spent on doing fundamental research. This has been 
evident at both Belleville and Brantford. As an example, at Brant- 
ford, erratic results were being obtained in terms of the trihalo- 
methane results from the pilot plant using a standard chlorine 
dosage. Conventional thought as noted by Stevens and Syroons (16) 
was. that given a free chlorine residual the maximum amount of 
chloroform would develop. At Brantford this was shown not to be 
the case (17). After considerable work it was determined that the 
maximum formation did not occur until well past the point of a 
free chlorine residual. The chloroform production does not level 
out until 30 rog/L free chlorine residual has been applied. Part 
of this may be a fiinction of the DAI measurement arr^ ♦-'-is is still 
to be investigated. Full discussion of this phenomenon will be 
presented in the Brantford report but suffice to say that fundamental 
problems such as this, make assessment of complex removal methods 
very difficult. 

The Brantford Project has attempted to assess the practicality 
of GAC in a retrofit situation in which major plant modifications 



209 



would not be necessary. The raw pilot plant data to date would 
suggest that the carbon in the filter would require regeneration 
in the neighbourhood of 3-40 days depending on the criteria of 
exhaustion used. Modifications to the front end of the pilot 
plant are now being assessed to lengthen the carbon life. 

In summation, an approach to dealing with contaminants 
has been outlined that includes: 

1) Assessment of risk, 

2) Analysis of methods-review and standardization / 

3^ Survey to determine the extent of the contaminant, 

4) Removal method to reduce or eliminate the contaminant if 
necessary. 

The chlorinated organics are merely the very tip of the 
organics iceburg and it is extremely important that a standardized 
rational approach be developed to handle new and exotic organic 
pollutants as they emerge. 

Dealing with the public concerns, having full technical informat- 
ion, avoids the problems of over extrapolation and misinterpretation 
which can happen when the brush-fire approach to dealing with micro- 
contaminants is teiken. 



210 



REFERENCES 



1) Hunsinger, R.B. , Drinking Water Pollution by less Well 

Known Contaminants, paper presented at the AWWA 
Atlantic Section (1979). 

2) Roberts, K.J., Assessment of Municipal Water Quality and 

MOE Requirements, paper presented at Urban Water Supply 
Conference, University of Toronto {19R0). 

3) The Analysis of Trihalonethanes in Finished Waters by the 

Purge & Trap Method, Method 501.1. US EPA Cincinnati, 
Ohio (1979). 

4) Guidelines for Canadian Drinking Water Quality, 1978. Health 

and Welfare, Canada (1980). 

5) Ontario Drinking Water Objectives, 1980. Ontario Ministry 

of the Environment, Toronto (in press). 

6) Nicholson, A. A., Meresz , 0., Organics in Ontario Drinking 

Waters, Part I, paper presented at the Pittsburg 
Conference of Analytical Chemistry and Applied Spectro- 
scopy (1976). 

7) Smillie, R.D. , Nicholson, A.A. , Meresz, O. , Duholke , W.K., 

Rees, G. A. V.^ Roberts, K.J., Fung, M.C., Organics in 
Ontario Drinking Waters, Part II, Ontario Ministry of 
the Environment (1977). 

8) Pfaender, F.K., Jonas, R.B. , Stevens, A.A., Moore. L. , Mass, 

J.R. , J. Environ. Sci. Technol . 12, 438-441 (1978). 

9) Peters, C.J., Young, R.J., Perry, R. , J. Environ. Sci. Technol. 

14, 1391-1395 (1981) * 

10) Martin, G.W., Survey of Ontario Drinking Water for Haloforms, 

t Ont£irio Ministry of the Environment (personal communication) . 

11) Schalekamp, M. , Bakker, S.P. , Effluent and Water Treat. J. 

January (1978). 

12) Fung, M.C., Reduction of Haloforms in Drinking Water Supplies, 

Report #69, Ontario Ministry of the Environment (1978). 

13) Simmons, R.A.G., "Chloroform Reduction Investigation Programme 

at Belleville Utilities Cormission" , Report to the 
Ontario Ministry of the Environment (1979). 

14) Love, O.T., Carswell, J.K., Miltner, R.J., Symons, J.M. Treat- 

ment for the Prevention or Removal of Trihalomethancs in 
Drinking Water. Appendix 3 to "Interim Treatment Guide 
for the Control of Chloroform and Other Trihalomethanes", 
US EPA. 



t\\ 



15) Simmons, R.A.G. , "Chlorine - Disinfection Effectiveness 

and THM Control", paper presented at the AWWA Ontario 
Section meeting (1980). 

16) Stevens, A.A. , Symons, J.M., Formation and Measurement 

of Trihalomethanes in Drinking Water. Proceedings - 
Control of Organic Contaminants in Drinking Water - 
US EPA (1980). 

17) Edwards, K.L. , Oberski, D.G. Organic Contaminant Removal 

Trial of Granular Activated Carbon at City of Brantford 
Water Supply (in press) . 

18) Gillies, M.T., Drinking Water Detoxification, Noyes Data 

Corp. Park Ridge, New Jersey, U.S.A. (1978). 



212 



Viruses and 

the Environment - Goff Jenkins 



Virology Scientist 
Laboratory Services Branch 
Ontario Ministry of the Environment 



November, 1980. 



I 



213 
VIRUSES AND THE ENVIRONMENT 



Human and animal viruses are minute infectious agents that range in 
size from 20-250 nanometers. The typical virus particle consists of a nucleic acid 
core surrounded by a protein coat. Consequently, a virus particle in solution 
behaves as a polyelectrolyte, bearing a net positive charge at acidic pH's below its 
isoelectric point, and a net negative charge at pH's above its isoelectric point. This 
property is important in recovery methods for viruses. The virus particle adsorbs 
to charged surfaces under suitable conditions, and can subsequently be eluted. 

A virus in the environment, for example, in sewage or water, behaves 
as a charged particle, adsorbing freely to particulate matter or to other viruses. 
This factor plays a major role in the removal of viruses during sewage treatment 
because adsorbed virus particles may be precipitated out and aggregated in the 

sludge. 

Over one hundred different viruses are known to be excreted in 

human feces (1). A number of these viruses are resistant to conventional 

wastewater treatment plant procedures, and are capable of remaining viable in 

water for long periods of time. Since a single infective virus particle may be 

capable of inducing infection and disease in a susceptible host, the presence of any 

viruses in a water supply poses a potential health hazard (2). 

The viruses of prime concern, from an environmental viewpoint, are 
the enteric viruses. There are approximately 108 known enteric viruses (1) (Fig.l). 
These viruses are capable of multiplications within the gut, and may be excreted in 
concentrations as high as 10^ - 10^^ particles/g of human fecal material (3). 

Documented syndromes that may be induced by enteric virus 
infections range in severity from colds, fever and diarrhea, to polio-like paralysis 
(1) (Fig. 2). A single type of virus can manifest itself in a variety of clinical 
symptoms, while the same symptoms can be produced by many different viruses. 
For example, aseptic meningitis may be induced by polioviruses, echoviruses, 
coxsackieviruses, and other enteroviruses. 



214 



FIG. 1 - ENTERIC VIRUSES OF HUMAN ORIGIN 



VIRUS GROUP 



NUMBER KNOWN 



1. Enteroviruses 

Polioviruses 
Echoviruaes 
Coxsackieviruses 

Other 



3 

31 

29 

4 



2, Adenoviruses 

3. Reoviruses 
ii. Hepatitis A 

5. Hepatitis B 

6. Rotaviruses 

7. Others 



31 
3 

1 
1 

1+ 
4 



TOTAL 



108 



215 



FIG. 2 - SYNDROMES IN MAN CAUSED BY ENTERIC VIRUSES 



ASEPTIC MENINGITIS 

PARALYTIC POLIOMYELITIS 

FEVER 

COLDS 

DIARRHEA 

HERP ANGINA 

MYOCARDITIS 

ACUTE RESPIRATORY DISEASE 

PHARYNGO-CONJUNCTIVITIS 

ACUTE HEMORRHAGIC CYSTITIS 

HEPATITIS LIVER INVOLVEMENT 

PARALYSIS (POLIO-LIKE) 

RASH 



216 



It has been estimated that over 60% of all human diseases are of viral 
origin (4). What is not knov/n is the percentage of viral diseases that are 
waterborne. For most virus infections, the source and route of infection can not be 

determined. 

The epidemiology of waterborne viral outbreaks has been difficult to 
elucidate, because disease symptoms may take weeks to appear, and most 
infections are subclinical or asymptomatic. In addition, efficient methodologies for 
the isolation and identification of the viruses of prime concern, namely the 
hepatitis A virus, the rotaviruses, and the Norwalk agent, have not been developed 

as yet. 

The Centre for Disease Control in Atlanta, in 1976, reported that the 
average annual number of waterborne disease outbreaks (including viral and 
bacterial outbreaks) is increasing Crig. 3) (9). Although only one-third of the known 
enteric viruses can be cultivated |n vitro , much of the increase shown in Fig. 3 is 
due to improved detection methods for enteric viruses. 

Eighty-three hepatitis A outbreaks, attributable to drinking water, 
were reported in two papers published in 1967 and 1976 (5, 6). Numerous other 
waterborne outbreaks of "infectious hepatitis" have been documented in the 
literature (7, 8). When a comparison is made between the annual incidence of 
hepatitis A and typhoid fever in the United States from 1952 to 1972 (Fig. 4), it is 
evident that the number of cases of the bacterial disease, typhoid fever, has 
decreased with improved water treatment practices, whereas the number of cases 
of hepatitis A appears to be increasing (10). 

The most common human infection associated with a waterborne 
agent is nonbacterial gastroenteritis (11). The agents responsible for these 
infections will probably be shown to be viruses. Rotavirus, a recently discovered 
enteric virus, has been established as the major pathogen of nonbacterial infantile 
diarrhea throughout the world. Up to 10^^ Rotavirus partic!es/g of feces may be 
excreted by an infected individual. Laboratories world-wide are currently involved 



nC. 3 - AVERAGE ANNUAL NUMBER WATERDORNE DISEASE OUTBREAKS (IN UNITED STATES) 

1938-1975 



50 



m 

i 

Z; 

<. 
U 



40 



30 



20 



10 




1940 



1945 



1950 



1955 



1960 



1965 



1D70 



1975 



1^ 

-si 



FIG. 4 - ANNUAL INCIDKNCES OF INFECTIOUS HEPATITIS AND TYPHOID 

FEVER IN THE U.S. 1952-1972. 



xlO 



xlO." 



A 



/ V 



/ 



/ 



\ 



y 



X 



INFECTIOUS 
HEPATITIS A 



Q 

MX: 

Q 
O 

< 



xIO 



TYPHOID 



xlO 



1952 1954 



1956 



1958 I960 1962 1964 1966 1968 1970 1972 



I-* 
00 



219 



in the development of methods for the routine isolation and identification of human 
rotaviruses from the environment. The need for such a methodology was re- 
emphasized at the 1980 International Viruses and Wastewater Treatment 
Conference in England. A study by Cabelli on the incidence of swimming- 
associated gastrointestinal infection showed that a significant level of infection 
was incurred by swimmers in waters which were well within microbiological 
standards for body-contact recreation Cl2). The evidence presented suggested that 
rotaviruses could be the causative agent, but the virus was not isolated. 

In addition to the enteric viruses discussed so far, numerous others 
are of major concern. The enteroviruses, which include poliovirus, coxsackievirus 
and echovirus are excreted in substantial numbers in the feces of infected 
individuals for varying periods of time, with a mean duration of excretion for 

poliovirus of 50 days. 

It is now well documented that enteric viruses are capable of 
surviving standard sewage treatment processes and consequently may be released 
into the water through sewage effluents (13). The different stages of sewage 
treatment vary in their efficiency for their removal and/or inactivation of viruses 

(Fig. 5). 

A) Primary Sedimentation 

Since viruses in water are often associated with particulate matter, a 
number of them may be precipitated out during primary sedimentation. The 
removal rate is highly variable and the viruses may remain viable in the sediment, 

B) Biological Treatment 

Activated sludge treatment, trickling filters, and waste stabilization 
ponds vary greatly in removal efficiency. Under ideal conditions, activated sludge 
treatment is very efficient for the removal of most enteric viruses. However the 
variability of the environmental conditions present during activated sludge 
treatment, in many cases results in a greatly reduced virucidal activity. Trickling 
filters and stabilization ponds are even more erratic in their virus removal and 
inactivation efficiencies. 



RG^j - VIRUS ELIMINATING EFFICIENCY OF VARIOUS STAGES 
OF SEWAGE AND WATER TREATMENT 



220 



■ 



TYPE OF TREATMENT 



REMOVAL 
EFFICIENCY 



INACTIVATION 
EFFICIENCY 



1. PRIMARY SEDIMENTATION < 55% 



NONE 



2. BIOLOGICAL TREATMENT D-99% 



VERY POOR 



3. TERTIARY TREATMENT 



2-99% 



VARIABLE 



A. DISINFECTION 



0-99% 



0-99% 



221 



C) Tertiary Treatment 

Tertiary treatment is effective for the removal gf viruses. It is capable 
of removing 99.999% of all viruses under ideal conditions. However the virus 
particles may remain viable and accumulate in the sludge, and consequently 

remain a hazard. 

The addition of lime to raise the pH of sewage sludge to between 11,0 and 
11.5 has been found efficient for the removal and inactivation of enteric viruses 
(14). This procedure was used at the Woodstocl< sewage treatment plant to prevent 
the spread of polioviruses during the poliomyelitis outbreak in 1978. 

D) Disinfection 

Traditionally, chlorination has been the major means of disinfection in 
North America. The virucidal action of chlorine is dependent upon such factors as 
the chemical nature, pH, and temperature of the material being treated. Large 
amounts of organic matter are present in the effluents from activated sludge 
plants. Consequently, large reductions of infectious viruses are not attained 
because of the combination of the chlorine with ammonia and organics. Further 
complicating the problem is the wide variability in resistance of different enteric 
viruses to inactivation by chlorine. In a study of the resistance of 25 human enteric 
viruses with 0.5 mg free chlorine residual, the time required for 99.99% 
inactivation varied from two minutes to two hours (15). Viral susceptibility to 
inactivation by chlorination is pH dependent, and the pH of sewage effluents is not 
optimal for virucidal inactivation. As mentioned earlier,. virus particles in solution 
act as charged particles. Virus particles may aggregate and become absorbed to 
particulate matter. It has been shown that adsorbed virus particles are much more 
resistant to inactivation by chlorination than are unassociated particles. Conse- 
quently, the efficiency of chlorination is minimized even further. 

In summary, virus removal during sewage treatment is realized primarily 
through precipitation of the virus particle, and chlorine disinfection, as practised, 
is not efficient for the production of a safe virus-free effluent. 



222 



There is a growing concern about the potential health hazard posed by 
viruses in the environment. The need to assess this risk has become readily 
apparent in recent years. 

In a study supported by Provincial Lottery funds, Dr. Sattar in Ottawa 
developed the talc-celite procedure for the recovery of pathogenic human viruses 
from potable and surface waters (16). In phase I of his study, Dr. Sattar detected 
the presence of enteric viruses in 100% of all raw sewage samples, and in greater 
than 50% of chlorinated effluents and water samples collected at Brittania Beach 
(Fig. 6) (17). Forty percent of the samples of raw water collected at a Water 
Purification Plant were positive for enteric viruses. In addition, 9 out of 35 potable 
water samples exhibited evidence of transmissible cytopathic degeneration in tissue 
culture. The detection of morphological changes or cytopathic effect (C.P.E.) in 
tissue culture, is the first stage in isolating and identifying viruses. C.P.E.'s how- 
ever may be caused by agents other than viruses, such as mycoplasma, or they may 
be caused by toxic factors. Therefore the presence of viruses must be confirmed 
by electron microscopy or serological techniques. The C.P.E. in these nine samples 
was transmissible, indicating the C.P.E. was not due to toxic factors, but no virus 
particles could be detected under the electron microscope. This does not rule out 
the possibility of a viral etiology. 

In phase 11 of the study. Dr. Sattar analyzed samples from a Water 
Purification Plant, and from the Ottawa River, downstream of the Gatineau and 
Rideau Rivers (18). All 76 river samples were positive for virus, and 29% (11 of 38) 
treated water samples fnam the Water Purification Plant showed C.P.E.'s 
Preliminary electron microscopy showed the presence of virus-like particles. These 
data indicate the need to assess the risk associated with the presence of pathogenic 
viruses in potable waters. 



223 



FIG. 6 - RESULTS OF VIROLOGICAL TESTING FROM THE 



OTTAWA RIVER STUDY 



SAMPLE TYPE 



NUMBER OF 
SAMPLES 



NUMBER OF 
SAMPLES-POSITIVE* 



SEWAGE TREATMENT PLANT 



a) RAW SEWAGE 


23 


b) CHLORINATED EFFLUENT 


24 


OTTAWA RIVER 


76 


BEACH 


43 


WATER PURIFICATION PLANT 




a) RAW WATER 


59 


b) TREATED WATER 


63 


c) TAP WATER 


IP 



13 

76 
28 



39 

11** 



* POSITIVE - BY C.P.E. AND ELECTRON MICROSCOPY. 



** - OTHER SAMPLES SHOWED C.P.E. - NOT CONFIRMED BY E.M. 
*** - ONE SAMPLE EXHIBITED C.P.E. - NOT CONFIRMED BY E.M. 



224 



The Ontario Ministry of the Environment has developed the capacity to 
perform environmental virologicat analyses, and is currently participating with the 
University of Toronto in an epidemiological study of selected bathing sites in 
Southern Ontario. A portion of this study is being supported by Provincial Lottery 
funds. 

In the first phase of this study, which was completed in the spring of 1980, 
selected bathing beach sites were sampled and analyzed for the presence of enteric 
viruses. A sewage treatment plant and its receiving waters in Southwestern 
Ontario were also examined. The first set of samples from the S.T.P. was 
collected in December 1979, while the plant was taking part in a chlorinaticxi study 
and the chlorination was shut off. The second set of samples was collected from 
the chlorinated effluent in mid-January, 1980. 

Five samples were collected at the sewage treatment plant during each 
survey (Fig. 7). Sewage pad samples were collected from the influent sewage line, 
end from the S.T.P. effluent after the chlorine contact chamber and before the 
effluent pipe. Forty litre grab samples were collected from the discharge end of 
the effluent pipe, and from the receiving waters upstream and downstream from 
the discharge. 

The electron microscopic identification of the virus isolates was carried 
out by the Electron Microscopy Department of the University of Toronto and the 
Water Quality section of the Ministry of the Environment. 

Twenty-two beach-site samples were analyzed in the first stage of the 
study. Viruses were not detected in any of the samples. However, all ten samples 
collected from the sewage treatment plant and the receiving waters were positive 
for viral cytopathic effects on tissue culture (Fig. 8), 

While the chlorination was shut off, enterovirus particles were recovered 
from the influent pad sample and the effluent grab sample. Reovirus particles 
were recovered from the effluent pad sample, and the i^Dstream and downstream 
receiving water samples (Fig. 9). 



225 



RG. 7 - SEWAGE TREATMENT PLANT SAMPLING 



INFLUENT 
SEWAGE 



■>- 



EFFLUENT 
PIPE 



S.T.P. X 



> 



O 



o 



RECEIVING 
RIVER 



O 

X = SAMPLING LOCATION (SEWAGE PAD) 
O = SAMPLING LOCATION (AO L. GRAB) 



na 8 - RESULTS OF SAMPLING 



226 



SAMPLE TYPE 



NUMBER 
OF SAMPLES 



NUMBER 
POSITIVE 



SURFACE WATER 
(BEACH) 



11 



SEDIMENT 
(BEACH) 



11 







SEWAGE PAD 



SEWAGE EFFLUENT 
(GRAB SAMPLE) 



SURFACE WATER 
(RIVER) 



227 



FIG. 9 - RESULTS OF SEWAGE TREATMENT PLANT SAMPLING 



A. CHLORINATION OFF 



SAMPLE TYPE 



CELL CULTURE E.M. IDENTIFICATION 

DIAGNOSIS 



SEWAGE INFLUENT 
(PAD) 



EMTEROVIRUS 



SEWAGE EFFLUENTT 
(PAD) 



REOVIRUS 



SEWAGE EFFLUENT 
(GRAB) 



ENTEROVIRUS 



RECEIVING WATER - UPSTREAM 



RECEIVING WATER - DOWNSTREAM 



REOVIRUS 
REOVIRUS 



228 



All five samples collected at the sewage treatment plant with 
chlorine disinfection in operation were also positive for viral cytopathic effects in 
tissue culture (Fig. 10). Electron microscopic and serological identification has not 
been completed on these isolates. 

In the second phase of the study carried out during the summer of 
1980, seventy-seven samples from selected bathing beaches, recreational waters, 
and sewage treatment plants were analyzed for the presence of enteric viruses. 
Sewage Treatment Plants in St. Catharines, Toronto, and Port Hope, beaches in St. 
Catharines and Wasaga, and selected conservation areas were sampled. First 
passages have been completed on all samples. Evidence of viral presence is evident 
in several samples, and confirmation through E.M. and serological techniques is 

currently underway. 

Concurrent with the epidemiological study, the M.O.E. virus 
laboratory is constantly refining the procedures used for recovering enteric viruses. 
We are currently assessing automated sampling and processing equipment as 
described by Dr. Payment (19). The use of positively charged cartridge filters with 
improved virus adsorption capacity as described by Sobsey are being evaluated (20). 
Standard methods for virological analyses should be established within two years. 

We are also establishing the capacity to analyze potable water 
samples. The talc-celite method of Dr. Sattar will be one of the systems 
evaluated. Drinking water sample processing must be automated and of a 
continuous flow type due to the large sample volume, 1000 litres. 

It now appears likely that rotaviruses will be found to have a 
waterborne etiology, and the significance of this will be understood when the 
incidence of rotavirus infection in the population can be properly assessed. If, as 
Cabelli suggests, rotaviruses turn out to be the prime agent involved with 
swimming-associated gastrointestinal infection, it becomes essential to develop thp 
capacity to recover rotaviruses from the environment and cultivate them m vitro 
so this risk may be properly assessed. 



229 



FIG. 10 - RESULTS OF SEWAGE TREATMENTT PLANT SAMPLING 



B. CHLORINATION ON 



SAMPLE 



CELL CULTURE E.M. IDENTIFICATION 

DIAGNOSIS 



SEWAGE INFLUENT 
(PAD) 



N.D. 



SEWAGE EFFLUENT 
(PAD) 



N.D. 



SEWAGE EFFLUENT 
(GRAB) 



N.D. 



RECEIVING WATER -UPSTREAM 



N.D. 



RECEIVING WATER - DOWNSTREAM + 



N.D. 



230 



As the procedures for recovering enteric viruses are improved and 
refined, they may be used to study the virus removing efficiency of selected 
sewage treatment plants. As stated earlier, chlorination, as normally practised, is 
inadequate for the generation of a safe effluent. Studies need to be done to 
establish the best means of producing a virus-free effluent. 

Finally, studies need to be designed to properly assess the risk posed 
by the presence of viruses in the environment. The viruses of concern must be 
clearly identified, methods must be available or developed for their recovery from 
the environment, and epidemiological evidence should be gathered to ascertain 
what levels of virus pose significant health problems. Such epidemiological studies 
are complex and require a great deal of man power, but they are essential if we are 
to establish meaningful criteria for safe virus levels in recreational and/or potable 
waters. 



231 



Bibliography: 

1) Melnick, J. L. (1978), "Water as a Reservoir of Virus in Nature and Means for 
Control", in Viruses and Environment, E. Kurstak and Karl Maramorosh (Eds.), 
New York. Academic Press, pp. 203-226. 

2) Plotkin, S. A. and Katz, M. (1967). "Minimal infective doses of viruses for 
man by the oral route", in Transmission of viruses by the water route, G. 
Berg (Ed.), New York, John Wiley and Sons, pp. 151-166. 

3) Editorial (1975), Rotaviruses of man and animals. Lancet,], pp. 257-259. 

4) Horsfall, F. L. (1965). "General Principles and Historical Aspects", in Viral 
and Rickettsial Infection of Man", F. L. Horsfall and I. Tamm (Eds.), 
Montreal: Lippincott Co., pp. 1-10. 

5) Mosley, J. W. (1967). "Transmission of viruses by drinking water", in 
Transmission of Viruses by the Water Route, G. Berg (Ed.), New York: John 
Wiley and Sons, pp. 5-23. 

6) Goldfield, M. (1976). "Epidemiological indicators for transmission of viruses 
by water", in Viruses in Water, G. Berg et. al. (Eds.), Washington, D.C.: 
Amer. Pub. Hlth. Assoc, pp. 70-85. 

7) Bryan, J. A., Lehmann, J. D., Setiady, E. F. and Match, M. H. (1974). "An 
outbreak of hepatitis A associated with recreational lake water". Amer. J. 

Epidem. 99, 145-154. 

8) Dennis, J. M. (1959). "1955-56 infectious hepatitis epidemic in Delhi, India", 
3. Amer. Water Works Assoc, 5]_, pp. 1288. 

f) Center for Disease Control (1976). Food and Waterborne Disease Outbreaks: 
Annual Summary 1975. U. S. Department of Health, Education and Welfare 
Publication No. (CDC) 76-8185. 

McDermott, J. H. (1974). "Virus problems and their relation to water 
supplies", J. Amer. Water Works Assoc, 66, pp. 693-698. 



232 



11) Sattar, S. A. (1978). Viruses, Water and Health. University of Ottawa Press. 
Ottawa, Ontario, Canada. 

12) Cabelli, V. J. (1980). As reported at Viruses and Wastewater Treatment, 
International Symposium, Surrey, England. Sept. 15-17, 1980. 

13) Berg, G. (1973). "Removal of viruses from sewage, effluents, and waters. 1. 

A review". Bull. W.KO., 49, pp. 451-460. 

14) Sattar, S.A.. Ramia, S. and Westwood, J. C. N. (1976). "Calcium hydroxide 
(lime) and the elimination of human pathogenic viruses from sewage. Studies 
with experimentally-contaminated (poliovirus, type 1. Sabin) and pilot plant 
samples.", Can. J. Pub. Hlth., 67, pp. 221-226. 

15) Liu, O. C. and McGowan, P. (1973). Effect of chlorination on human enteric 
viruses in partially treated water from the Potomac River estuary - Study 
report prepared for the U.S. Army Engineer Division, North Atlantic. 
Northeastern Water Supply Laboratory, Narragansett, R.I. 

16) Sattar, S. A. and Westwood, J. C. N. (1976). "Comparison of talc-Celite and 
polyelectrolyte 60 in virus recovery from sewage: development of technique 
and experiments with poliovirus (type 1, Sabin) - contaminated multi-litre 
samples". Can. J. Microbiol., 22, pp. 1620-1627. 

17) Sattar. S. A. (1979). Viral Pollution of the Ottawa River and its possible 
impact on the quality of potable and recreational waters in the Ottawa area - 
Phase II. Final Report for the Ontario Ministry of the Environment Research 
Study Contract No. 77-004-11. 

IB) Sattar, S. A. (1978). Viral Pollution of the Ottawa River and its possible 
impact on the quality of potable and recreational waters in the Ottawa area - 
Phase I, M.O.E. Contract No. 77-004-11. University of Ottawa, Ottawa, 

Ontario. 
19) Payment, P. and Trudel, M. (1980). "A simple low cost apparatus for 
conditioning large volumes of water for virological analysis", Can. 3. 
MicrobioL, 26, pp. 548-550. 



233 



20) Sobsey, M.D. and Glass, J.5. (1980). "Poliovirus concentration from tap 
water with electropositive adsorbent filters", App. and Env. Microbiol., 40, 2, 
pp. 201-210, 



234 



BRUCE AND PICKERING 
THERMAL PLUME 
DEFINITION FLIGHTS 



An Application of Thermal Sensing Techniques 

by 

Intertech Remote Sensing Ltd. 



4.0 



235 



TABLE OF CONTENTS 



Page No. 



1. INTRODUCTION 

2.0 DATA ACQUISITION SYSTEM 
ZA Sensor Platform 

2.2 Sensor 

2.3 Data Storage 

3.0 DATA PRODUCTION SYSTEM 



METHODOLOGY 

4.1 Fundamental Principles 

Thermal Infrared Linescanners 
and Processing 



4.2 
4.3 
4.4 



Imaging 
Imagery 



5.0 CONCLUSIONS 



ABSTRACT 



Intertech Remote Sensing Ltd., funded by a grant of the Provincial 
Lottery Trust Fund administered by the Ontario Ministry of the 
Envirorenent provi ded airborne data acqu i si ti on servi ces usi ng an 
i nf rared 1 i nescanner to map the wi ntertime synopti c thermal pi ume 
characteristics off the Bruce Nuclear Power Development site on Lake 
Huron. In addition, Intertech acquired imagery of the water borne 
thermal plume from the Pickering "A" N.G.S. site on Lake Ontario. 

The imagery was acquired using a Daedalus Enterprises thermal 
infrared linescanner, equipped with a detector sensitive to emitted 
thermal radiation in the 8-14 micrometer portion of the electro- 
magnetic spectrum. The output signals from the linescanner were 
recorded on an Instrumentation tape recorder for subsequent labora- 
tory processing. 



236 

1.0 INTRODUCTION 

The imagery collected by an airborne thermal infrared linescanner 
represents surface radiation emitted from a scene as viewed by the 
scanner. The resulting thermal image is a two dimensional thermal 
display, with no depth information directly available to the inves- 
ti gator. The radiated energy viewed by the scanner is not only a 
function of the temperature of the scene, but is also affected by 
the emissivity characteristics of the material being viewed. Modern 
linescanners are capable of providing quantified data to the inves- 
tigator by utilizing calibrated thermal reference sources as a 
benchmark to which the thermal content of the viewed scene is 
compared. Quant it at i ve scanner temperatures are referred to as 
apparent surface temperatures. Additional procedures (not under- 
taken during the present study), including ground measurements and 
atmospheric modelling Are required to convert image temperatures to 
absolute ground temperatures if required. Buoyant water borne 
thermal plumes can be easily imaged by linescanners to provide 
synoptic information on plume shape, direction and areal extent. 

2.0 DATA ACQUISITION SYSTEM 

2.1 Sensor Platform 

The sensor was installed in a twin engined, non pressurized modified 
Cessna 411. Intertech currently operates two aircraft with airborne 
infrared linescanners in Canada (Ottawa and Calgary). 

2.2 Sensor 

The sensor used was a single channel Daedalus Infrared Linescanner 
Model 1230, operating at a scan rate of 60 scans/ second. The 
detector used was sensitive to radiation in the 8-14 micrometer 
portion of the electromagnetic spectrum and provided a spatial 
resol uti on of 1.7 mi 1 1 i radi ans ( at nadir) and a thermal resol uti on 
of 0.2CO. The configuration of the scanner provided ar) across 
track field of view of 77 . 20 ( unvi gnetted ) . The scanner was 
solidly attached to the airframe and corrected for instabilities in 
the roll axis of +/-50 from horizontal . The sensor was equipped 
with calibrated black body thermal reference sources. 

2.3 Data Storage 

The signals generated by the scanner were recorded on a Weston- 
Schl umber ger Sangamo Sabre 6 i nstrumentation tape recorder, 
operating at a recording speed of 30 inches /second. The recording 
medium was Ampex 1" Magnetic Instrumentation tape. 

3.0 DATA PRODUCTION SYSTEM 

The hard copy imagery of the series of overflights was generated on 
the analogue processing facility of the Canada Centre of Remote 
Sensing in Ottawa. The processing f acil ity consists of the fol- 
lowing major components: 

1. 3-M Mincom Instrumentation Tape Recorder 

2. Daedalus 2 Channel Analogue Processor, Model 612 

3. Daedalus Field Printer, Model 617 



237 



The output products consisted of 127 run. wide format continuous roll 
film processed i n two different modes . One set of anal ogue mode 
imagery was produced which presents the thermal 
densities on film which vary in direct proportion 
of the recorded thennal signal. Analogue imagery 
with respect to the black body reference sources, 
imagery in the 8-Level Sliced Mode was produced which presents the 
thermal data as six stepped gray shades on film, along with clear 
and black film to indicate thermal signal levels below and above the 
selected thermal signal range. 8-Level Sliced imagery are quanti- 
fied with respect to black body reference sources. 



data as varying 

to the intensity 

is not quantified 

A second set of 



4,0 



METHOOLOGY 



4.1 



Fundamental Principles 



All matter above absolute zero (QOK) emits radiant energy in 
proportion to its temperature (Figure 1). As the temperature of an 
object increases the intensity of the radiant emissions increase and 
the peak of the radiant emission curve shifts towards the shorter 
wavelengths. In the electromagnetic spectrum, a temperature related 
progression exists from the thermal infrared to the near infrared, 
through the visible and into the ultra violet portion of the spec- 
trum (Figure 2). Modern detectors of radiant emissions are selected 
according to the portion of the spectrum in which their detectivity 
is at an optimum level (Figure 3). The choice of a detector is 
partially determined by the temperature of the matter to be detected 
as it defines the portion of the spectrum in which radiant emissions 
will occur. The earth has a surface temperature of 300° K for 
most practical purposes. At that temperature, a black body radiant 
emitter has an emission curve that peaks at 9.7 micrometers. The 
detector chosen to image matter close to the ambient temperature of 
the earth should, therefore, be sensitive to the emissions at or 
near to 9.7 micrometers. 



m 



e> 1.0 Blackbody 

e*0.9 Graybody 
^^--c>f<A) Spectral Attenuating Body 




Wavelength; X 



Figurel Spectral Distribution (For e.i;0.9&f(x)) 



To utilize airborne thermal sensors, atmospheric attenuation should 
be at a minimum. In the thermal infrared portion of the spectrum 
CO2, H2O and O3 are major attenuating agents, blocking radiant 
emissions at specific wavelengths. However, two large transmission 
windows exist between 8 to 14 micrometers in the long wave and 3 to 
5 mi crometers i n the s hort wave porti on of the thermal 1 nf rared 
spectrum (Figure 4). 



238 



Visible Light- 



rSun;6000°K 

^Tungsten Filament ;3000''K 
Red Hot 0biect;800°K 
rEarth;300*'H 

Dry lce;195<'K 
Liquid;Air 79^K 




Wavelength ; |im 



Figure 2 Spectral Blackbody Emittances 



Theoretical Maximum D* Detector 

4.2'K GeCu 

30® K GeHg 

77" K In Sb(PV) 

195* K In As 

300" K PbS- 




Wavelength ; pm 
^-Thermister Bolometer 300° K & Pyroelectric J 

Figure 3 Long Wave Sensitivity & DetectorTemperature 




— O3 Attenuation 



H-iO 



Figure 4 Atmospheric Transmission 



239 



4.2 



Thennal Infrared Linscanners 



An infrared linescanner uses a spot detector (HgCdTe at 

generate a voltage proportional to the radiant emissions 

onto the detector. This analogue voltage 

magnetic tape. A scan line is imaged by 

which reflects into the optical elements 

emissions from a line directly below the 

to the direction of flight (Figure 5). 

anal ogue vol tages produced by the detector with reference to the 

rotation of the scan mirror defines the field of view of a scanner. 

The forward motion of the sensor platform ensures that the next scan 

line created acquires new data in the along track direction. 



780K) to 

f ocussed 

is amplified and stored on 

a rotating angular mirror 

of the scanner the radiant 

aircraft and perpendicular 

Electronic gating of the 



Aircraft 



Path 




IF0V.>IFOV„ 



Figures Infrared Line Scanning 



In a quantitati ve scanner, bl ack body reference sources are intro- 
duced on each si de of the field of view. These reference sources 
are calibrated so that any desired temperature will be radiated by 
them and included in the recorded analogue signal. With one black 
body set below the minimum detected radiant emission from a scanned 
scene and the other black body set above the maximum, it is possible 
to assi gn equi val ent bl ack body radi ant temperatures to the 
bracketed thermal scan by linear interpolation techniques (Figure 6). 



Max. Interpolation Errors: 



E 'I 



.2 * 



for fe-14)- 
(org-51— 


-* 


J^ 




(g-l^m (3 






i 


!,„-.'-' 


/ 








^,,5,..--^ 




^ 






..;::^;=^ 


=^ 




^ 




^^^ 






^ 1 


Z^^^ 


.„.--*^ 












— 




^--;:;*'^ 










--;;^ 


--^ 








^- '1^:^^ — * 








— — — T*" 
















1 







O-Ejiim 



Blackbody Temperature in C 



Figure6 Linear Interpolation Errors 



240 



4.3 



Imaging and Processing 



To construct an image of the recorded thermal scene, the printer 
sweeps each individual scan line across a cathode ray tube. The 
i ntensi ty of the detected radi ant emi ssi ons i s proporti onal to the 
anal ogue vol tages recorded on tape. These vol tages determi ne the 
brightness of the cathode ray tube face. The sweep rate across the 
tube face is proporti onal to the acqui si ti on scan rate ( i ncl udi ng 
S-bend correction). Film is transported across the CRT face perpen- 
di cul ar to the scan across the CRT and the f i Im dri ve speed is 
determined by the acquisition V/H ratio, to reconstruct an accurate 
image of the sensed thermal scene. 



For quantitative processing of data, the voltage values of 
bodi es are sampl ed el ectroni cal ly and hel d f or reference 
The voltage range defined by the 
even divisions. Analogue voltages 
whichever of the six divisions is 
7). If the voltages fall outside 



the black 

purposes. 

bl ack bodies is divided into six 

of each scan line are forced into 

closest to them in value (Figure 

the defined black body range, two 



other di visi ons i ndi cati ng over and undershoots are avai 1 abl e. The 
film exposed by this process shows clear to indicate radiant emis- 



si ons below the 1 ow temperature 
above the high temperature black 
radiant emissions falling within 
Since the calibrated temperatures 



is possible to assign equivalent bl ack 
ranges to each of the six gray shades. 



bl ack body; bl ack for emi ssi ons 
body; and six shades of gray for 

the range of both bl ack bodies, 
of the black bodies &rQ known, it 
body radi ant temperature 



Srablv Pulse 




BB1 



Set 1-7 



Figure? 8- Level Slicing 



4.4 



Imagery 



Flight lines were chosen to give the best synopti c view of the 
plumes on the parti cul sr date of the overflight. In total , seven 
sets of winter imagery were collected. Four flights were conducted 
over the Bruce Nuclear Power Development on Lake Huron (March 12, 
April 2, 16 and 17, 1980) and three flights over the Pickering 
Nuclear Generating Station on Lake Ontario (March 12, April 6 and 
17, 1980). Due to editorial constraints, limited imagery are shown 
here and interested parties are invited to contact the MOE liaison 
officer for further details. 

Figure 8 is a selected example of the near field thermal plume off 
the Bruce A N.G.S. This imagery was acquired on April 17, 1980 at 
an altitude of 1829 m (A.S.L.) at 10.47 hrs (EST). Data were 
processed in level slice mode with darker tones corresponding to 
cooler temperatures and lighter tones corresponding to warmer 
temperatures. PI ant i ntake and discharge temperatures during the 
time of the flight were 2.4 and U.IOC, respectively (Ontario 
Hydro operations data). The image frame is approximately 2.8 km x 
3.5 km. 



241 

5.0 CONCLUSION 

Airborne thermal infrared mapping systems offer an excellent cost 
effective method to acquire and display information on thermal 
plumes. Airborne thermal IR data provide: 

(1) information related to plume size, shape and orien- 
tation; 

(2) a synoptic overview; and, 

(3) a product that is easy to interpret. 



2A2 




Figure 8 Bruce A N.G.S. Thermal Plume April171980 



243 



THE PICKERING 'A' THERMAL PLUME 

DURING THE WINTER MONTHS. SOME PRELIMINARY 

RESULTS FROM A CO-OPERATIVE STUDY 



R. R. Weiler 
Lake Systems Unit 
Water Resources Branch 
Ministry of the Environment 

November, 1980 



244 

- 1 - 

1.0 Introduction 

From December 1979 to the end of March 1980 the thermal plume from 
the Pickering Nuclear Generating Station A was studied by Ontario 
Hydro, National Water Research Institute and the Water Resources 
Branch, Ministry of the Environment. Staff from the Ontario Centre 
for Remote Sensing (Ministry of Natural Resources), the Regional 
Municipality of Durham, Metro Toronto and the Ministry of Labour 
provided additional support. 

The objectives of the study were to characterize the behaviour of 
the thermal plume in winter by mapping its extent, shape and 
duration, under different meteorological and current conditions, and 
to characterize the dispersion characteristics of the nearshore 
zone. 

The Pickering Nuclear Generating Station is located on the north 
shore of Lake Ontario, about 36 km east of Toronto (Figure 1.0 - 
1). Its four CANDU heavy water generating units are rated at 540 MW 
each. The once-through cooling water (maximum 114 m'^/s, actual 
90-100) is drawn from Lake Ontario through a 300-meter long channel 
between groins and Is discharged through an open channel about 250 
west of the intake. The designed temperature rise through the 



m 



on 



cooling condensers is 11 c. A second similar nuclear stati 
(Pickering B) is near conpletion irrmediately to the east of and 
adjacent to A. It will use the same intake channel, but the 
discharge will be on the east side of the site. 

This paper, which describes some of the preliminary findings on the 
temperature regime near Pickering, is based on calculations and 
interpretation by the Ministry of the Environment of data collected 
and processed by Ontario Hydro, NWRI and the Ministry. A more 
complete analysis is expected in 1981. 



245 



2.0 Methods 

2.1 Plume Surveys 

On 8 occasions (January 29, February 5, 8, 12 and 20, March 4 and 
20, April 1, 1980) Ontario Hydro measured temperature profiles in 
the plume using bathythermographs from boats (Ontario Hydro, 1980b). 

The Ontario Centre for Remote Sensing (OCRS, 1980) flew infra-red 
radiometric surveys of the plume on 6 occasions (February 7, 12 and 
28; March 6, 19 and 26, 1980). A PRT-5 infra-red sensor, which in 
sensitive to temperature changes of 0.1 C and has an absolute 
accuracy of + 0.5°C, was used to measure the surface temperature. 

2.2 Bottom Temperatures 

Bottom thermographs were moored at sites shown on Figure 1.0 - 1. 
The instruments were located at the 5-meter contour east and west of 
Pickering A and on two transects east and west of the station. The 
thermographs used by Ontario Hydro have an overall accuracy of 
+ 0.2°C. The four thermographs supplied by MOE and moored 
furthest west have an overall accuracy of + 0.6°C. A data base of 
hourly temperature readings from all the thermographs was 
established by Ontario and used in further analysis. 

2.3 Currents 

Fifteen current meters were moored at locations shown on Figure 1.0 
- 1 by NWRI, Ontario Hydro and Ministry of the Environment. Two 
CATS platforms, fitted with bottom current meters and thermistor 
chains for temperature profiling, were installed at the Pickering 
and Ajax water intakes. All instruments, except three, gave almost 
continuous records for the whole period (NWRI, 1980). 



246 



3.0 Results 

3.1 Meteorological Conditions 

The winds blew chiefly from the northwest quadrant (58% of the time) 
with NW and NNW being the predominant directions (40%) and from the 
opposite quadrant for only 14% of the time. Resultant wind for the 
whole period was to 133°. The predominant speed range was between 
10 and 20 km/h (50%). The distribution of wind directions and 
speeds does not differ markedly from those of previous years. 

The winter was somewhat milder in December and January than average, 
with the average air temperature being 2.5°C and 1.5°C, 
respectively, above the 10-year means of -2.8°C and -6.1°C. In 
February, the average dropped to -7°C or 2° below the mean. 
Milder conditions returned in March and April when temperatures were 
slightly higher than average. As a result the onset of true winter 
conditons was somewhat delayed and less ice than usual was observed 
along the shore. 

3.2 Currents 

The two predominant current directions are 70° and 250° - that 
is, east and west along the shoreline. Examples of currents 
averaged over a month are shown in Figure 3.2 - 1. This basically 
bi-directional current pattern holds In a band from 1 km to 12 km 
from shore, with the frequency of eastward currents (to 70°) 
varying, at different moorings, between 33% and 58% and westward (to 
250 ) between 14 and 34%. The mean current speeds in this band 
averaged 10-23 cm/s to the east and 7-16 cm/s to the west. The 
frequency and speed of currents increased from the shore to about 
3-5 km. after which they remained essentially constant. At moorings 
closer to the shore, its configuration has a greater effect. For 
example, at 79-00-21A the eastward currents occur only 15% and 
westward only 20% of the time, the average speeds are around 7 cm/s 
and the predominant current direction is towards the shore (NWRI, 
1980). This pattern of bi-directional currents offshore was also 
observed at Pickering by Ontario Hydro in the winter of 1979 (60% to 
the east, 9% to the west). 



247 



The Study period can be divided basically into alternating episodes 
of eastward and westward current, with a few episodes of currents in 
other directions. The change in direction occurred over a very 
short time, generally of the order of less than 12 hours. Fig. 3.2 
- 2 shows 2 westward and 3 eastward current episodes and the effects 
on temperature as measured at bottom thermographs. 

The first easterly period starts on December 28 and ends on January 
2; the second starts on January 7 and ends on January 15; the third 
starts on January 18. The start of each episode is preceded by a 
period of slower currents ( 5 cm/s). The direction of the winds and 
the currents are roughly similar, although the second easterly 
episode is interrupted by periods of westerly winds. The direction 
of the winds is much more variable than that of the currents. 

In general, eastward episodes dre associated with warm temperatures 
as the plume impinges on the thermographs east of Pickering. The 
temperature does not decrease irmiediately after the current switches 
on January 2, but decays rather slowly to an average around 2°C, 
interrupted by periods of higher temperature. At the start of the 
third eastward period, there is a rather abrupt temperature increase 
and the plume front travels along the current until, by the time it 
reaches THB 27, it is no longer present. Although plume impingement 
on a particular location is closely linked to plume direction, it is 
also clear that residual temperature effects can occur and that 
effects of the plume can be observed even when, to judge by the 
currents, the plume is going in the opposite direction. 

3.3 Plume Structure 

Figure 3.3 - la, (Ontario Hydro 1980b) shows an extreme eastward 
plume (March 4) observed during the study. Other examples of plumes 
are shown on Figure 3.3 - 4a and 4b. Based on the 3°C isotherm as 
the edge of the surface plume, the length of the observed easterly 
plumes varied from about 4 to 11 km with the majority being around 
5,5 km. The majority of westward plumes were less than 3 km long. 
The plumes were surprisingly narrow. In only two cases did the 
eastern plume exceed 2 km in width and the most cofimon width was 
less than 1 km. The westerly plumes were somewhat wider. 



248 



The plume width at the bottom was somewhat greater than at the 
surface, though with long plumes the spreading is not large. Figure 
3.3 - lb gives the cross section of the March 4 plume at the A-A 
transect about 2.5 km from the outfall. The plume is close to being 
isothermal vertically and the lakeward edge has the characteristics 
of a front; that is. the temperature changes rapidly over a small 
distance. The near field structure can be much more explicated, as 
exemplified by a plume mapped on February 26, 1979 by Ontario Hydro 
(Figure 3.3 - 2a, b; Ontario Hydro 1979). Although a sharp front 
exists with the temperature dropping from more than 5°C to less 
1 C at the surface over a few decameters, once the water has 
cooled below 4 C, the water spread along the bottom following the 
density gradients. 

Between 1973 and 1979, Ontario Hydro (1980a) surveyed the Pickering 
NGS plume on 15 days and NWRI on 9 days between the months of 
December and April when the ambient lake temperature was less than 
4 C. They observed eastshore plumes on 423i of those days (under W 
to NW winds), wests hore plumes on 25% (winds from SE quadrant), 
offshore plumes on 17% (NNW to ENE winds), split plumes on 8% (SW 
winds), and plumes shifting from one shape to another on S% of the 
survey days. Along their centre lines the cold weather plumes had 
temperatures above 4°C from surface to bottom. At plume leading 
edges, water had cooled to 4°C and below, sunk, and spread out 
along the bottom In the direction of plume movement underneath the 
ambient lake water. Along their sides, the cold weather plumes had 
steep horizontal temperature gradients and were almost isothermal 
vertically. Some sinking and spreading along the lake bottom was 
also observed at the sides of the plumes. Hydro's surveys did not 
go far enough from the outfall to define completely the extent of 
many of the cold weather plumes surveyed. 

The only day when both Ontario Hydro and OCRS measured the plume was 
February 12, 1980. Although different in detail, the overall 
structures are the same (Figure 3.3 - 3a, b; Ontario Hydro 1980b, 
OCRS 1980). 



249 



3,4 Plume Impingement Along the Shore 

The length of time the lake temperatures as measured by the bottom 
thermographs (5 m depth) are above the ambient can be used to trace 
the extent and frequency of occurrence of the plume. This method 
assumes that an ambient temperature can be selected and that there 
are no other major localized sources of heat besides the Pickering 
generating pi ant. 

Ambient temperatures were derived by averaging the lake temperatures 
measured by thermographs which were not affected by the plume; that 
Is, from either the three or four most easterly or westerly 
thermographs when the currents were to the west or to the east, 
respectively. Once the ambient was established, accurate to within + 
0.5 C, a four hour average temperature difference was used in 
computing the duration of temperature above ambient. A few examples 
of the duration-time curves are shown in Fig. 3.4-1. 

The major river runoff period starts 1n the latter part of March and 
in early April, Indeed, the temperature patterns measured during 
the plume surveys of March 20 and April 1 show the effects of runoff 
at the mouths of Highland Creek and the Rouge River. Solar 
radiation will affect only a very thin surface layer and will affect 
the nearshore region uniformly. Further, as shown by the 
thermograph records for the east and west transects, the nearshore 
temperatures are significantly cooler than further offshore, a fact 
which may be attributed to the smaller depth and the proximity to 
the shore. The flow from the York-Durham sewage treatment plant 
outfall is around 10 MGD or 0.5 m /s, a very small fraction of the 
90-100 m /s put out by Pickering. Therefore, it Is unlikely that 
there are other major localized sources of heat besides the 
generating plant. 

The percent of time temperatures were 0.5, 1, 2, 3, and 4 degrees 
Celsius above ambient were read from temperature-duration curves 
such as 3.4-1 and plotted as a function of distance from Pickering 
on Fig. 3.4-2a and 2b. A difference of 1.0 degrees is probably 
significantly different from the ambient. 



250 



It is clear from Fig. 3.4-2a and 2b that differences greater than 
two degrees can be observed as a significant percent to the time 
( >25«) only close to the station; that is. closer than 5 km to the 
east and 1.5 km to the west. Temperature differences greater than 
this are confined to even smaller distances. Temperature rises of 
one degree are observed 5 to 10% of the time at the maximum 
distances - 17 to 20 km - where the thermographs were moored. 



L 



251 



4.0 Summary and Conclusions 

The currents In the period mid-December to end of March are 
basically parallel to the shore and predominately to the east (30 - 
605i of the time) rather than the west (15 - 35%). Maximum speeds 
can reach 45 cm/s, although the average is around 15 - 20, The 
currents increase out to about 5 km and remain thereafter fairly 
uniform out to 12 km. Csanady (1970) has called such currents 
"coastal jets". Near shore, topographical features such as 
headlands will form localized subsidary circulation patterns. 

Because the currents are chiefly shore parallel and swift, the 
effects of the Pickering thermal effluent can be detected at 
considerable distances on both sides of the generating plant. Using 
1 C as a significant rise above ambient lake temperatures, the 
effluent can be traced as far as 15-20 km east and west of the 
station 5 - 10% of the time in the winter. Temperature rises 
greater than 2 C can be observed a significant percent of the time 
{ >25%) only close to the station; that is, closer than 5 km to the 
east and 1,5 km to the west. 

The Ministry of the Environment is continuing its analysis of the 
results of the thermal plume studies to determine their significance 
for water management in coastal areas. 



252 

Acknowledgement 

The author wishes to thank R. Walker, R. Arden and R. Farooqui, from 
the Design and Development Division, Ontario Hydro, for processing 
data on temperatures, currents and winds measured by Ontario Hydro 
for this study. He also wishes to thank J. Bull and R. Murthy of 
the National Water Research Institute, Canada Centre for Inland 
Waters, for processing data on currents and temperatures measured by 
NWRI. 



References 

Csanady, G. T. 1970. Dispersal of effluents in the Great Lakes. 
Water Res. 4: 79-114 (1970). 

Ontario Centre for Remote Sensing (OCRS), Ministry of Natural 

Resources, 1980. Infra-red radiometric survey over the 
Pickering Nuclear Generating Station. 17 p. and appendices, 

Ontario Hydro, Design and Development Division. 1979. Lake Ontario 
Pickering NGS 'A': Thermal plume investigations - cold 
weather plume surveys February 1979. Report No. 79440. 
3 p. and di agrams. 



-. 1980a. Lake Ontario. Pickering Generating Station: 
Analysis of thermal plume surveys conducted 1971 to 1979. 
Report No. 80072. 31 p. and appendices. 



. 1980b. Lake Ontario. Pickering Nuclear Generating 

Station: Winter thermal plume study 1979-1980. Thermal 
plume mapping. Report No. 80294. 9 p. and diagrams. 

National Water Research Institute, 1980. Coastal current 

climatology sunmary, Pickering Generating Station Dec. 6, 
1979 to Mar. 31. 1980. 12 p and appendices. 



PICKERING WINTER PLUME STUDY— 1979-80 INSTRUMENT LOCATIONS 







-MOE d -5 



"h 



Pickering nJciear 




^ r\ generating station 




NTHB12-5 { \ i } 
\ ,X*^Si5^rHB19-5r' AJAX 




5 


/^^ ^Ai^J 


rj 


, THB 16-5-^ r^^^ ^^— ^ 

CM06-12 • . a\ , „ 


> /^ 




\ 


• f 21A-8 


THB25-5 


• 




•^ ^ 




^16A-12 




29 ^ 





WHITBY 



A 

I 

THB 27-5 



QiHAWA 



LEGEND 

A THB16-5 V LAK,t 

MOE 2 -5 ^thermograph station & depth{m) 



ONTARIO 



• CM06-12 



16A 



V Current meter station & depthcm) 
-12 / 







T — r-1 

4km 



Figure 1*0-1 






MOORING: 16, 21 DATE: FEB 
MONTHLY SUMMnRYrCURRENT- 



1980 "4 



79-00-21 
0.75km from shore 



CURRENT 

0-5 CM/SEC 

= 5-15 CM/SEC 
■=J i 15 CM/SE 



. . CROSS LftKE 
1160) 




^ RLONO LRKt 

^ no i 



DEPTH <29 M 



K DIRECTION T0HRR08 



FIGURE 3.2-1. 



255 



N 360 



S 180 



U 



WIND DIRECTION TO 




Iu7 



Ky 




H -^^-"^V ' V^ /J / T^^^"^ 




23 

DEC. 1979 



FIGURE 3.2-2. 



Wind direction and speed at Pickering 'a'* 
current speed and direction at mooring CM06 
(l2m depth); temperature at bottom thermographs 
THB16 ( 1.2 kmE of Pickering 'A'), 19 (4.7 Km), 
25 (9.7 km) and 27 ( 17.2 km), all at 5 m depth, 
for the period Dec. 23,1979 to Jan. 23, 1980. ' 



i 







"'c. 



^<-'?/, 



'♦f . r 




mW OlRECTKHI TO onJ SPEft) (*.»i/>il 
CUMCNT DIMCTION TO S"^ S>>CtD<(« 
OH-I . 

OM-IJ 

aiR rEMPEMTURE t*C) 

dtUlTIVE HimOfTT 1%) 

BIROMtTmC WCSSUBC (IP«1 
KET (UOtATION ( W/p*) , . 

VATER HJRFACE ELEVATION- CGO (•) 
BROS! RLANT OUTPUT |U«). 
MJUBER or UMITS OPERATINS 
tNTAKE TEMPERATURE |*C ) 
OyTr*U TEMPERATURE ft). 
CONDENSER COOLIM WATER 
rLOWRATE l»Vi I 



M 



|tNt i>| 

[ToV] 



(7« U 



IO«l 



CA 



Q£T] 




PICKERING NGS 



THERMAL PLUME INVESTIGATION 

WATER TEHPERATURC AT SUHrACE 
DATE MAR. 4, (910 TIME 10 OS UH'SSEST 



a 



Ontario Hydro 

design 8 consiruciion branch 
hydroultc ttudiei & development 



I 



KILOMETERS 



FIGURE 3.3-1 fl 







400 



100 



1200 1600 2000 

HOBIZONTftl. DISTANCE IN METRES 



2400 



2600 



LEG END 

t 




SURFACE TEMPEBAIURE ' C 
BOTTOM TEMPERATURE " C 



PICKERING N G S 



THERMAL 
PLUME INVESTIGATION 

WATER TEMPERATURES AT 
DATE MAR. 4, 1980 TIME I 



SECTION A-A 
2 to II4B EST 




Ontario Hydro 

design ft construction branch 
hydroulic studies 8 development 

FIGURET.-»-5t 



O"*" 





I iO l> M 

riHC IN HOURS 



CO » M 



WIND 



LEGEND 



tlCTIOH 
LOCATION 



^^ 



ft rOIITlON NUUIII 
H ■ ■■ 



PICKERING "a" GS. 



THERMAL PLUME INVESTIGATION 
SURFACE WATER TEMPERATURE 
26 FEB. 79 TIME-1323 to 1651 EST 



a 



Ontario Hydro 

design 8 construction branch 
hydraulic studies 8 development 

FIG.3.3-2a 



Si 




LgQCHD 

( 
X 





SUfirACE TCHPERATURC "C 
BOTTOM TEMPERATURE «C 



3000 



BOO 



1000 1900 2000 

HOnrZONTAL DISTANCE IN HETREt 



2B00 



PICKERING 'A' G.S. 



THERMAL PLUME INVESTIGATION 
SECTION E 
WATER TEMPERATURE 
26 FEBRUARY, 1979 



a 



Ontario Hydro 

design 6 construction branch 
hydroulic studies & development 
I FIG.3.3-2b 






+ 



FIGURE 3. 3-3 a 

PHT5 INFRARED RADIOMETRIC SURVEY 

FEBRUAR V I2.I9B0 
10 A.M. 




+ 



+ 



+ 



V 



+ 



tooo 



500 



tooo 



ME tflti 
OHTARO 'CENTBE tW REMOTE SE-^SiNG 

OnTARiO MiNisrnr OF NAfuRftL RCSCl.'BCCS 



•!■-•" fl *-- V'C^liC OarA IN Df:nE£S CtiCrUS 




KILOMETERS 



FIGURE 3. 3 -3b 



2 



WIND DIRECTION 'to' ond SPEED (kra/hj 
CURRENT DIRECTION 'TO' and SPEED (cm/i) 
oH-8 r ... 

0H-I2 

AIR TEMPERATURE (*'C) 

RELATIVE HUMIDITY (7o) 

BAROMETRIC PRESSURE (kPa) 

NET RADIATION (W/m*) 

WATER SURFACE ELEVATION-CGD (m)... 

GROSS PLANT OUTPUT (MW) 



SEII 



ENEI5 



E9 



-40 



66 



101-67 



168 



NR 



2137 



5 8 



NUMBER OF UNITS OPERATING \_A 

INTAKE TEMPERATURE (^C ) 

OUTFALL TEMPERATURE {"C )....... . 

CONDENSER COOLING WATER 

FLOWRATE (mVs ) ■ • , 

NR - NO RECORD 



16-7 



97-4 



ON 



PICKERING N.G.S. 



THERMAL PLUME INVESTIGATION 

WATER TEMPERATURE AT SURFACE 
DATE FEB. 12, 1980 TIME 09M6 to 15:23 EST 




Ontario Hydro 

design & construction branch 
hydraulic studies 6 development 



262 



12 



E 



o 



10 



•« q 







i 



50- 




263 



5 10 

DISTANCE EAST OF PICKERING 



< 

Al 

t- 
< 

UJ 



7 



50- 




T 
5 10 

DISTANCE WEST OF PICKERING 



IS 



20 



km 



Figuie 3.4-2 



Duration of Temperature rise AT= T - Tarnbient f*^) 

as a function of distance from Pickering for +0,5 ^aT^ 4.0 



264 



The Uptake of Methylmercury^*^^ by 
Walleye ( Stizostedion vitreum vitreum) 
through a Simulated Ecosystem as a 
Function of Selected pH Regimes 



Watson, T.A.^, J.S. Langan and T.J. Wheaton 



MacLaren Engineers Planners & Scientists Inc 

Suite 100 

1220 Sheppard Avenue East 

Willowdale , Ontario 

M2K 2T8 



Present Address: Department of Biological Sciences 
Simon Fraser University 
Burnaby, British Columbia 
V5A 1S6 



265 



ABSTRACT 

The uptake of methylmercury^*^^ in walleye ( Stizostedion vitreum vitreum) 
and rainbow trout ( Salmo qairdneri ) from water and diet was investigated 
over a period of five days at pH 5.0, 6.0 and 7.0 in four stainless 
steel columns (1ms 4.5 m) of 3500 L capacity. 

Relative accumulations of methylmercury^*^^ by walleye and trout were 
monitored in fish that were: (l)-starved; (2) -fed methylmercury^^^ 
labelled food; and (3) -fed unlabelled food. Rainbow trout were tagged 
with methylmercury^^-* which was added to their water and zooplankton 
forage base ( Daphnia magna ) . Methylmercury^*^^ was added to the columns 
or ecosystem simulators as methylmercuric^"^ chloride to yield a final 
approximate concentration of 4 ng/L in the vessels. 

Daphnia (D^ magna ) acquired greater amounts of methylmercury^*^^ at pH 
7.0 compared with those at pH 6.0. Rainbow trout also accumulated the 
most methylmercury^*^"^ at pH 7.0 and uptake was linear during a five day 
exposure. Methylmercury^^^ accumulation was the highest in trout fed 
labelled Daphnia while those deprived of Daphnia accumulated roughly 
one- third the quantity of feeding trout. The relative contributions of 
methylmercury^^^ to trout from water and food was of the same magnitude. 

Uptake of methylmercury^^^ by walleye from trout was not affected by pH. 
Walleye fed methylmercury^^^ tagged trout accumulated twice as much of 
the isotope compared with fish that were starved or fed with unlabelled 
trout. Less than 15% of the amount of methylmercury^^^ in trout fed to 
walleye was retained while the remaining 85% was presumed to have been 
eliminated. Acidity did not affect the retention or elimination of 
methylmercury^*^^ . 

Results of this study suggest that methylmercury uptake by fish in 
acid-stressed waters may not be greater than for those in pH neutral 
areas. This observation may be related to a slower elimination rate of 
the compound by aquatic organisms in pH neutral environments. 



ACKNOWLEDGEMENTS 

Appreciation is extended to Dr. A. Niimi and Messrs. K. Suns, G. Craig, 
C. Innis and D. Rodgers for their support and criticisms. We would also 
like to express our gratitude to the White Lake Hatchery of the Ontario 
Ministry of Natural Resources for supplying the walleye used in this 
study. The assistance of Mr. Dave Troubridge is appreciated for con- 
ducting bioassays of Daphnia magna tolerance to acidity. 



266 



INTRODUCTION 

The effects of mercury contamination and acid precipitation on the 
aquatic environment are currently receiving a great deal of attention. 
Mercury is perhaps the most ubiquitous of the toxic heavy metals in the 
aquatic environment, but it is generally found at low (ng/g or fjg/L) 
concentrations (Huckabee et. al. , 1975). The causes of acid precipi- 
tation have their roots in the present and historical uses of fossil 
fuels, especially coal, for energy. Acid precipitation is formed in the 
atmosphere where emitted compounds of sulphur, chlorine and nitrogen are 
converted to sulphuric, hydrochloric as well as nitrous and nitric acids 
(Likens et al. , 1979). 

The movement of mercury in the aquatic environment is significantly 
affected by its methylation in sediments followed by methylmercury ' s 
entry into every trophic level of the aquatic ecosystem (Jernelov and 
Lann, 1971) . Methylmercury is concentrated in aquatic organisms by 
direct uptake from water and diet, with the latter route apparently 
being the most important (Norstrom et al. , 1976; Phillips and Russo, 
1978; Phillips and Buhler, 1978). There is a tendency for predator fish 
and organisms at higher trophic levels to contain the greatest amounts 
of methylmercury (Jernelov and Lann, 1971; Krenkel, 1974). 

Acid precipitation has caused great economic and aesthetic losses in the 
aquatic environment due to the extirpation and reduction of fish popula- 
tions. Increased acidity causes a general decline or reduction in 
numbers of fish species with some of the more desirable species being 
affected over a pH range as high as 5.5 to 6.0 while others show toler- 
ance to a range as low as 4.5 to 4.7 (Harvey, personal communication). 
Primary productivity does not appear to be affected by acidity, although 
a simplification of phytoplankton communities has been reported 
(Kwiatkowski and Roff, 1976). The tolerance of zooplankton to increased 
acidity appears to be quite limited as Daphnia pulex do not reproduce 
below pH 7.0 (Davis and Ozburn, 1969). Sprules (1975) found that many 
species do not occur below pH 5.0 in acid stressed lakes, similar obser- 
vations have been reported by others (Carter, 1971; Salazkin, 1971; 
Harvey, 1975; Roff and Kwiatkowski , 1977). 

Acid precipitation has been known to kill fish in field situations. 
Fish kills have been reported after periods of heavy rain and spring 
snowmelt due to the acid pulse in receiving waters (Leivestad and Muniz, 
1976; Leivestad et al. , 1976). The prolonged impacts of acid preci- 
pitation and declining pH seem, however, to have their greatest effects 
on fish recruitment. Recruitment failure may occur as a result of 
acid- induced mortality of fish eggs and/or larvae (Schofield, 1976). 
Mortalities in early life stages can alter the average age of fish 
populations and shift the size and age structure to larger and older 
fish (Ryan and Harvey, 1979). The direct effects of acid- induced mor- 
talities to eggs and larvae have been demonstrated in a number of labora- 
tory studies (Johansson et al . , 1973; Mount, 1973; Menendez, 1976; Craig 
and Baksi, 1977) . 

The impacts of acid rain have attained a new significance with the 
observation that the toxicities of various metals such as aluminum, 
zinc, cadmium, lead, arsenic, copper and mercury are increased as a 
result of declining pH (Schindler, 1979; Suns, personal cummunication) . 



267 



Schindler has stated, in fact, that concentrations of certain metals 
have been reported in Scandinavian lakes at levels which are within two 
to three times the values that have been shown to have toxic effects on 
fish. 

The increasing tendency for acidification of receiving waters by acid 
precipitation may have implications on the uptake and bioaccumulation of 
methylmercury through the aquatic food web. Increased acidity affects 
the partitioning of methylmercury between water and sediments. Miller 
and Akagi (1979) found, for example, that the amount of methylmercury in 
the water increased as pH decreased. This decrease in pH did not, how- 
ever, affect the total amount of methylmercury generated in the sedi- 
ments. Miller and Akagi (1979) suggested that these observations could 
quantitatively explain the elevations in mercury levels of fish taken 
from lakes of low pH. Suns et al. (1980) have also observed that fish 
in acid-stressed lakes exhibit higher concentrations of the metal due to 
depressed pH. The effect of pH on mercury uptake has also been inves- 
tigated in the laboratory. Tsai et al. (1975) exposed fathead minnows 
( Pimphales promelas ) and emerald shiners ( Notropis atherinoides ) to 
various concentrations of mercuric chloride in water and found that 
mercury uptake increased as pH decreased, with uptake increasing sharply 
at pH values below 7.0. 

It is apparent that our understanding of mercury movements and accumu- 
lations through aquatic ecosystems has increased in recent years. With 
the addition of acid inputs, however, we are now faced with a completely 
different dimension of mercury transport in aquatic environments, one 
which we do not fully comprehend. It is obvious that research must be 
undertaken to characterize the movements of the metal's various forms 
through aquatic organisms as a function of depressed pH. The most 
important chemical form in this respect is the methylated species in 
view of its high affinity for biological tissues (Phillips and Russo, 
1978). 

This study was designed to investigate some aspects of methylmercury 
transport and accumulation through an aquatic food chain as a function 
of depressed pH. In this study methylmercuric^*^^ chloride has been 
added to an aquatic ecosystem which has been simulated in large (1 m x 
4.5 m) stainless steel columns of 3500 L capacity. The research was 
carried out at the Great Lakes Biological Laboratories at Burlington, 
Ontario. Water samples used in the experiments were collected from 
selected lakes in the Muskoka region of Ontario. These lakes demon- 
strated physical and chemical parameters typical of lakes that are 
subject to the effects of acid precipitation. A representative array of 
organisms was chosen for specific trophic levels in the simulated eco- 
systems and included: primary producers (indigenous algae); zooplankton 
or primary consumers ( Daphnia magna ) ; a secondary consumer, rainbow 
trout ( Salmo gairdneri ) ; and a top predator or tertiary consumer, wal- 
leye ( Stizostedion vitreum vitreum) . The uptake of methylmercury^^^ 
from water by these organisms was evaluated. 



268 



MATERIALS AND METHODS 

Selection of Study Lakes 

All of the lakes considered as potential candidates were within the 
Muskoka-Haliburton region of Southern Ontario. The main criteria for 
selection of study lakes was their susceptibility to the effects of acid 
precipitation and accessibility. Lakes affected by acid precipitation 
are typified by poor buffering capacity and characteristically display 
low hardness and alkalinity levels. Lakes within the Muskoka-Haliburton 
region exhibit relatively low pH and have depressed alkalinities ranging 
from 14 to 200 |jg/L (Dillon et al., 1977). 

Selection of the lakes was initially accomplished by studying topogra- 
phical sheets to locate lakes of similar size and geographical place- 
ment- Data collected in previous years on pH, alkalinity, location, 
climatic factors and morphometry for selected lakes were also considered 
in the selection process. 

Based on the above criteria, a list of 15 potential lakes was derived 
and each lake was visited in January 1979 to obtain data on accessi- 
bility, physiochemical properties and topography. Water samples were 
taken through the ice at a depth of 0.5 m with a Kemmerer sampler. 
Samples were analyzed for heavy metal content (cadmium, copper, lead, 
zinc and mercury) and total dissolved solids. Analyses were performed 
by atomic absorption spectrophotometry. Measurements of pH, alkalinity 
and hardness were also determined. Acidity was measured with a portable 
pH meter (Fisher Accumet , Model No. 150) and hardness and alkalinity 
were estimated according to Rand et al. (1976). 

Collection and Maintenance of Experimental Organisms 

Phytoplankton, indigenous to the study lakes were used in this study. 
However, pure stock cultures of the phytoplankton, Chlorella vulgaris 
were used to maintain Daphnia magna prior to placement in the ecosystem 
columns. The Daphnia were obtained from the Great Lakes Biolimnology 
Laboratories (GLBL) at Burlington, Ontario and were maintained in de- 
chlorinated Lake Ontario water at 18-25°C. 

Rainbow trout (mean weight §1 g) were purchased from Goosen' s Trout 
Farm, Otterville, Ontario. The trout were maintained in dechlorinated 
Lake Ontario water at 15-18°C and compressed air delivered a supply of 
oxygen to the holding tanks. Two trout from this population were sacri- 
ficed for mercury analysis to monitor background concentrations prior to 
use of the stock in the uptake experiments. The fish were fed ad 
libitum on a commercially prepared diet (Martin Feed Mill Co., Elmira, 
Ontario) . 

Walleye (mean weight =12 g) were donated by the White Lake Hatchery of 
the Ontario Ministry of Natural Resources (Perth, Ontario) and were 
maintained under conditions similar to those described for the rainbow 
trout. The walleye would not accept pellet food, consequently they were 
fed ad libitum with either young rainbow trout or a locally purchased 
baitfish ( Notemigonus crysoleucas ) . One walleye was sacrificed to 
monitor the background concentration of mercury prior to use of these 
fish in the experiments. 



269 



Acid Toxicity to Daphnia 

The pH sensitivity of Daphnia was investigated m acutely lethal bio- 
assays prior to use in the ecosystem simulators. Daphnia which were: 
(a) fed rhlorella and (b) deprived of the phytoplankton were exposed to 
a pH range from 5.0 to 7.0 at 18°C in 250 mL Erlenmeyer flasks. The 
bioassay procedures roughly followed those described by Sprague (1973). 
Mortalities were monitored over 192 hours and were expressed as a cumu- 
lative percentage- 

Lake Column Simulators 

Lake column simulators are stainless steel, cylindrical, high volume, 
indoor enclosures, that simulate open-water conditions in a lake. The 
columns used at GLBL are 4.5 m high, 100 cm in diameter and have a 
volume of 3500 L. Light is supplied by a 1000 W tungsten-halogen lamp 
on a 12 h photoperiod. Further details of the simulators have been 
described by Hodson and Millard (1977). 

Isotope 

Methylmercury as methylmercuric^*^^ chloride (CH^^^^HqCl2) was obtained 
in two separate shipments from New England Nuclear, Boston, Massachu- 
setts. 

Isotope shipments were diluted with distilled water to specific activi- 
ties approximating 10 pCi/mL and stored under refrigeration in rubber- 
stoppered Wheaton glass serum bottles wrapped in aluminum foil. 

The relative amounts of organic to inorganic mercury in both shipments 
were determined by phase separation (Rodgers, personal communication) . 
Standard reference solutions of known methylmercury^*'^ concentration 
were prepared for each shipment. These standards were monitored for 
radioactive decay on a regular basis and a decay curve was calculated 
for each set. These standards were used to estimate methylmercury^'^'^ 
levels in water and animals during the experiment. Estimates of radio- 
active methylmercury are given throughout the text as methylmercury^*^^ 
and not as the chloride salt of the compound. 

Experimental Protocol 

Nine methylmercury^*^'^ uptake experiments were conducted using lake water 
samples from Atkins, Wood and Walker Lakes. 

Samples of lake water (3000 L) were collected using chemically inert and 
clean equipment provided by the Ministry of the Environment (MOE). Lake 
water was subsequently transported by tanker to GLBL, generally within 
12 hours. Water volumes in the columns were made up to 3500 L by the 
addition of deionized water prepared to simulate the water quality 
indigenous to the study lake. 

Five days prior to addition of methylmercury^^^, walleye (12-30 g) and 
rainbow trout (1.0-1.5 g) were caged and placed in the columns for 
acclimation to experimental conditions. Cages were fabricated from 6.8 
litre plastic pails with ports covered by fibreglass screening of ade- 
quate diameter to preclude access by Daphnia magna , yet sufficient to 
permit water cycling. Feeding was facilitated through an aperture with 



270 



a removable cover. Cages were weighted and suspended in the coliimns at 
depths ranging from 1 to 4 m. 

Nine walleye were introduced to each column. Experimental feeding con- 
ditions were as follows: 

(a) Three walleye were individually caged and fed during the experiment 
with rainbow trout previously exposed to methylmercury^*-'^^ through 
their diet and column water. The trout were weighed and counted 
for methyljnercury^*^''^ activity prior to presentation to walleye. 
This group of walleye was referred to as "Hot fed" ; 

(b) Another group of three walleye was placed in a single cage and fed 
during the experiment with rainbow trout which had not been exposed 
to methylmercury^*^^ . This group was referred to as "Cold fed" ,- 

(c) A final group of three walleye was placed in a single cage and 
starved during the experimental period. This group was referred to 
as "Starved". 

Rainbow trout were placed only in the pH 6.0 and pH 7.0 columns as they 
would not survive the pH 5.0 regime. Feeding conditions of the "hot 
fed" walleye at pH 5.0 were, therefore, satisified with rainbow trout 
which had been exposed to methylmercury^'^'^ in the pH 6.0 treatment 
columns. 

Each pH 6.0 treatment column received 18 rainbow trout while each pH 7.0 
treatment column received 9. Rainbow trout and walleye were fed their 
regular stock-tank diets on the first and third days of the 5 day accli- 
mation regime. 

After the five day acclimatory period, Daphnia representing all free 
swimming stages were added to the pH 6.0 and pH 7.0 columns. Columns of 
the pH 6.0 treatment received 6.0 g (wet weight) of the Daphnia while 
columns of the pH 7 . treatment received 3.0 g. No Daphnia were placed 
in the pH 5-0 column as they would not survive. 

Each experimental column was sampled for chlorophyl a content prior to 
dosing with methylmercury^*^"^. Chlorophyl a determinations followed the 
spectrophotometric technique (Trichromatic Method) outlined in Rand et 
al . , 1976 . Optical densities were measured on a PYE UNICAM SP1800 
spectrophotometer . 

ColiMns were dosed with stock solutions of methylmercury^'^^ to effect a 
water concentration of approximately 4 ng/L. This concentration has 
been shown to approximate "natural" background concentrations (Norstrom 
and Brounstein, 1974) . The CH3Hg^^^ stock solution was injected by 
syringe and capillary tubing into the intake pipe of the column recir- 
culation system. The dosing apparatus was rinsed many times to ensure 
complete isotope delivery. 

Water samples (5 mL) were taken at and 2, 4, 6, 24, 48, 72, 96 and 120 
hours after isotope addition to monitor the fate of methylmercury^'^^ in 
the columns during the experiment. Samples were counted in a Nuclear 
Chicago gamma scintillation counter (Model No. 18725) equipped with a 
sodium iodide crystal and a 3.18 cm sample well. 



271 



Uncontaminated distilled water in standard glass gamma counting tubes 
was used to estimate background levels of radiation. The background 
radiation count was taken as the mean counts per minute observed over 
nine minutes of monitoring. 

Water samples were compared to previously prepared standard solutions. 
The 5 ml sample volume proved to be the most efficient quantity as it 
would completely fill the counting well when placed in standard glass 
gamma counting vials. These vials were used for all water samples. Each 
water sample was counted for one minute nine separate times, whereas 
standards were counted three times for one minute each. The mean number 
of background counts was calculated for these data. Calculation of 
methylmercury^*^^ activity was related to a time which represents the 
assay day of isotope as defined from the decay of the standard solu- 
tions. 

During the course of the experimental period dissolved oxygen was moni- 
tored with a YSl dissolved oxygen meter calibrated against a Winkler 
standard (Rand et al. , 1976). Dissolved oxygen was typically above 75% 
saturation. 

Adjustments in pH and water temperature were made as required. Gener- 
ally, water temperatures remained relatively constant (18± 1°C), while 
pH values were ±0.3 pH units for each treatment. 

Twenty- four hours after dosing, approximately 20 Daphnia magna were 
sampled from each pH 6.0 and pH 7.0 column. The Daphnia were placed in 
Bouins fixative (Humason, 1972), and counted for mercury^^s activity. 
Sample activity was assessed from the mean of nine one minute counts. 
Phytoplankton samples were also taken at this time and processed for 
autoradiographical localization of methylmercury^^^^ Subsequent to 
plankton sampling, rainbow trout were released to forage ad libitum on 
Daphnia in the columns. 

Walleye feeding was initiated forty eight hours after addition of the 
methlymercury^*'^ isotope to the columns and was repeated at seventy two 
and ninety six hours. The feeding procedure is described below: 

"Hot fed" walleye from the pH 6 . and pH 7.0 treatments were 
fed with rainbow trout netted from their respective columns. 
"Hot fed" walleye in the pH 5.0 treatment were fed with rain- 
bow trout netted from the pH 6.0 column. All "Hot" rainbow 
trout were weighed, counted for mercury^*^^ activity in vivo 
and subsequently fed alive to the walleye. Counting rainbow 
trout in vivo was achieved by placing the fish head down in a 
standard gamma counting tube with 5 mL of well oxygenated 
fresh water and counting for one minute. After each counting, 
the trout were placed in a holding container with a larger 
volume of aerated water to recover from the stress of count- 
ing. The mean of three one minute counts was taken to repre- 
sent in vivo isotope activity. 

"Cold fed" walleye in all pH treatments were fed with rainbow 
trout from stock tanks which were not exposed to the isotope. 
These fish were not monitored for Hg^*^^ as preliminary count- 
ings on selected fish yielded similar counts as observed for 



272 



background levels. The exposure of "starved" walleye to Hg^*^'^ 
was limited to the ambient water in the individual columns. 

After 120 hours of column dosing all walleye were sacrificed with an 
overdose of MS 222 {ethyl m-aminobenzoate methanesulfonate) . Fish were 
subsequently weighed and then homogenized with a polytron tissue 
grinder. A weighed aliquot of the tissue homogenate (appromixately 
1 g), was placed in a counting tube and digested in 3 mL of 10% potas- 
sium hydroxide (KOH) . Sample counts were taken as the mean of three one 
minute counts . The remainder was frozen (-20°C) and forwarded to MOE 
for tissue analysis of total mercury content. 

Analysis of variance (ANOVA) and Duncan's comparison of means tests were 
performed on an APL computer (University of Guelph) on methylmercury^""* 
uptake in walleye as a function of pH and feeding regime. 

The ambient uptake of methylmercury^*^^^ by rainbow trout over a 120 hour 
period was investigated under exposure to pH 6.0 and 7.0 in a separate 
experiment. For this experiment, 6 rainbow trout were divided equally 
between the pH 6.0 and 7.0 columns of experimental replicate 3. 

These fish were retained in cages but were not permitted to feed. Trout 
were removed after 24, 48, 72, 96 and 120 hours and counted in vivo as 
described previously. Methylmercury^^^ uptake from the diet was ap- 
proximated from those fish which were feeding on Daphnia exposed to 
methylmercury^^^ after 48, 72 and 96 hours. 

Analyses of variance (ANOVA), covariance (ANOCOVA) , Student t-test, and 
regression were performed on APL computer (University of Guelph). 

Autoradiography 

Five hundred mL samples of phytoplankton were taken from the columns 24 
hours after dosing with methylmercury^'-'^ and processed based upon the 
methods described by Knoechel and Kalff (1976). The samples were agi- 
tated to disperse the phytoplankton homogeneously and a 15 mL aliquot 
from each sample was transferred to a 20 mL centrifuge tube. Each 
sample was centrifuged for 2 minutes at 500 rpm. A 10 mL aliquot of the 
supernatant was decanted off and replaced with 10 mL of tap water. The 
tubes were shaken to disperse the phytoplankton, and then centrifuged 
again for 2 minutes at 500 rpm. This procedure was repeated four times 
to remove water borne Hg^''^. Following the final rinse, all but 2 mL of 
the supernatant was decanted off and an aliquot of the remaining 2 mL 
was placed on acid cleaned slides and allowed to air dry. Air drying 
was preferred as it was less likely to cause rupture or deformation of 
the cell walls. Drying slides were placed in dust free boxes and were 
covered with a fine mesh phytoplankton webbing to prevent excess dust 
settling on the sample. When dry, the slides were placed in dust free 
dry microscope slide boxes and stored in preparation for autoradio- 
graphical localization of Hg^'^^. 

Specimens of Daphnia magna were sampled from the experimental columns 24 
hours after dosing with Hg^*^"^. These specimens were preserved in 
Bouin's fixative until processed for autoradiography (Humason, 1972). 
The fixed Daphnia were t insed of tlie Bouin's solution, dehydiated m an 
alcoliol sf t ies , taken through xylene cuid finally embedded in pai af f in 
wax following the methods of Humason (1972). 



273 



Embedded specimens were sectioned with a microtome to a thickness 
of 7 |j. Sections were placed on clean albuminised slides and allowed to 
dry. Wax was removed with xylene followed by hydration to water through 
an alcohol and water series (Humason, 1972). Sections were then stored 
in dry, dust free boxes until processed for the autoradiographical 
localization of Hg^*^^. 

After appropriate preparation, slides of plankton specimens were dipped 
in Kodak Nuclear Emulsion NTB3. The thickness of the emulsion layer 
varied for phyto and zooplankton. The emulsion was much thicker on the 
slides of the phytoplankton types since track autoradiographs of Hg^^^ 
emissions from specific cells were desired. In the case of the zoo- 
plankton, the intention was to localize the Hg^*^^ in various Daphnia 
tissues where grain density autoradiography is more aptly suited. Slide 
boxes were stored in a refrigerator and held at approximately ^°C while 
the latent image developed (Humason, 1972). 

Slides were removed at varying intervals and developed according to 
Humason (1972). After development, zooplankton slides were stained with 
methyl green and pyronin (Humason, 1972). Staining was not required for 
phytoplankton slides. 

Individual slides from all experimental groups were examined and repre- 
sentative photographs of plankton for each pH treatment were taken with 
a Zeiss photomicroscope (Model #4357006). 



274 



RESULTS 

Lake Selection 

Atkins, Wood and Walker Lakes were selected as the experimental lakes, 
their locations are shown in Figure 1. 

Atkins, Wood and Walker Lakes displayed pH ranges of 5,30-7.02, 6.5-7.0 
and 5.90-7 .25, respectively (Table 1) . The concentrations of heavy 
metals (Table 1) in these lakes were representative of uncontaminated 
lake waters (EPA, 1976; Enk and Mathis, 1977; Atchison et al . , 1977). 

Acid Toxicity to Daphnia 

As pH decreased, the mortality of Daphnia increased. The presence of 
food ( Chlorella vulgaris ) , however, reduced the mortality in a given pH 
treatment. Experimental pH values during the bioassay were 5.32, 6.31 
and 7.12. The trend to increasing mortality with a decrease in pH was 
maintained in both the fed and starved groups of Daphnia. No indivi- 
duals survived exposure at pH 5.32 although the mortality rate was more 
rapid for starved animals. After 192 hours, none of the starved Daphnia 
survived exposures to pH 6.31 while an attendant mortality of 60% was 
observed for grazing Daphnia. Near total mortality (84%) of starved 
Daphnia occurred at pH 7.0 while the rate was much lower for feeding 
animals (4%) . 

Background Mercury Levels in Trout and Walleye 

Mercury levels in trout and walleye were similar to those in uncon- 
taminated fish (Reeder et al. , 1979) and were below the Ontario Ministry 
of the Environment's (MCE) Standard of 0.5 Mg/g Hg. The mean concen- 
trations (wet weight) of these replicates for the two rainbow trout 
sampled were . 006 and . 005 pg/g Hg and for the single walleye was 
0.11 |jg/g Hg. Corresponding dry weight concentrations were 0.043 and 
0.03 pg/g Hg (trout) and 0.06 (jg/g Hg (walleye). 

Methylmercury^^^ Uptake Through the Simulated Ecosystems 

Upon dosing, methylmercury^^"^ rapidly distributed throughout the columns 
and was detectable in surface waters two hours after addition. Final 
concentrations in the column (± one standard deviation) were 2.99 ± 
0.54, 2.54 ± 2.01 and 2.35 ± 0.44 for pH treatments of 5.0, 6.0 and 7.0 
respectively. 

Algal biomass estimates of column water taken just prior to isotope 
dosing appear to indicate a trend toward lower algal biomass with in- 
creasing acidity (Figure 2). 

These biomasses were , however , adequate to sustain Daphnia in the 
columns for 96 hours based on a daily requirement of 10% of the total 
Daphnia biomass (wet weight). 

Methylmercury^*^^ was accumulated by Daphnia magna after 24 hours ex- 
posure in the column at pH 6.0 and 7.0 (Table 2). It appears that a 
greater amount of methylmercury^^^ is accumulated at pH 7.0 which ex- 
hibited a mean concentration per individual of 0.064 pg compared with 



275 



FIGURE 1 
LOCATION OF EXPERIMENTAL LAKES 






LATITUDE 


LONGTITUOE 


Wood Lalte 


45'00' 


79»05' 


Atkms Lake 


45''07- 


yg^M' 


Walker Lake 


4 5 "23' 


79'>05' 



TABLE 1 



CHEMICAL PARAMETERS OF SELECTED LAKES 



pH 



Total Dissolved Metals (mg/L' 







Enviro 


Lake 


CCIW 


clean 


Atkins 


5.95 


7.20 


Walker 


6.50 


6.70 


Wood 


6.70 


6.80 



MOE 













Total 










Hardness 


Dissolved 










CaCOa 


Solids 


Lead 


Mercur 


"Y 


Zinc 


(mg/L) 


(mq/L) 


<0.02 


<0.1 




<0.01 


5.50 


30 


<0.02 


<0.1 




<0.01 


7.00 


20 


<0.02 


<0.1 




<o.oi 


7.75 


24 



5.30 <0.005 <0.D2 
6.75 <0.005 <0.02 
5.90 <0.005 <a.02 






277 



pH 7.0 



TABLE 2 

CONCENTRATION OF METHYLMERCURY^f'S in 
Daphnia magna AFTER TWENTY- FOUR HOURS 



Total 
Replicate No CHaHg^o^ cHaHg^^^ 
Treatment No^ Individuals (ng) Individual Mean 

pH 5.0 (No surviving Daphnia magna at this pH) 

pH 6.0 

0.037 



Rl 


20 


0.583 


0.029 


R2 


15 


0.656 


0.042 


R3 


20 


0.820 


0.041 


Rl 


50 


1.226 


0.053 


R2 


20 


0.575 


0.030 


R3 


20 


2.200 


0.110 



0.064 



278 



FIGURE 2 

RELATIONSHIP OF pH AND COLUMN ALGAL BIOMASS' 

AT EXPERIMEf(T INITIATION AFTER NINE DAYS 

EXPOSURE TO EXPERIMENTAL pH REGIMES 



=\. 

CO 

CO 

< 

Q 
m 
_j 
< 



2S0 r 



200 



150 



100 



50 



D ATKINS LAKE 






O WALKER LAKE 




A 


A WOOD LAKE 








o 


/" 


° /- 


x^ 


A 


^^ 


o 
o 




^ 






;:a 






1 1 


. . 1 


|. 



45. 



50 



60 



70 



.pH 



■ALGAL BIOMASS ESTIMATED 

FROM CHLOROPHYL A MEASUREMENTS 

ACCORDING TO STANDARD METHODS (19771. 



279 



0.037 (jg at pH 6.0. Data for methylmercury^'^^ accumulation in Daphnia 
at pH 5.0 were not available as this pH regime was shown to be acutely 
lethal to the zooplankter. 

Total concentrations of methylmercury^*^'^ in feeding rainbow trout after 
48, 72 and 96 hours at pH 6.0 and 7.0 are presented in Table 3. 

The cumulative methylmercury^'^^ concentrations after 96 hours (sum of 
48, 72 and 95 hour levels) in trout are different (P<0.01, Student's 
t-test). The cumulative concentration (ng/g) of methylmercury^'^^ in 
trout at pH 7.0 (|J = 26.83 ng/g) was 65% greater than the level at pH 
6.0 (M = 16.25 ng/g) . 

Concentrations of methylmercury^*^^ over time for trout at pH 6.0 and 7.0 
and under different feeding regimes (Table 4, Figure 3) were different 
(P<0.05; ANOCOVA). Trout from pH 7.0 treatments had higher methyl- 
mercury^'^^ levels compared with those from pH 6.0 while feeding trout 
had higher concentrations than starved fish. 

The total amount of methylmercury^*^^ assimilated by walleye through prey 
(rainbow trout) is summarized in Table 5. No differences (P>0.05, 
ANOVA) were observed in the amount of methylmercury^^^ accumulated by 
walleye in the different pH regimes. A significant (P<0.05, ANOVA) 
feeding effect was, however, observed. Duncan's comparison of means test 
showed the mean methylmercury^*^^ concentration of walleye (1.26 ng/g) 
fed with labelled trout was greater than from the mean of starved wal- 
leye (0.60 ng/g) as well as those fed (0.71 ng/g) with unlabelled rain- 
bow trout. The latter two groups of walleye were similar in their 
methylmercury^o^ content (P>0.05, ANOVA). 

The ultimate concentrations of methylmercury^*^^ in individual walleye 
and rainbow are summarized in Table 6. These data were used to compare 
the amount of methylmercury^*^^ retained by walleye after having been fed 
with labelled trout. There were no differences (P>0.05, ANOVA) in the 
amount of methylmercury^^^ accumulated or eliminated by walleye. The 
approximate percentage retained for walleye in all pH treatments was 
8.00 with the remainder being eliminated. 

Mercury Levels in Post Experimental Walleye 

There was no significant difference (P>0.05, ANOVA) in the Hg concen- 
trations of walleye between replications in a given pH group nor between 
similar feeding regimes of the various pH treatments. The range of Hg 
concentrations (mean ± standard deviation) were from 0.11 ± 0.01 to 0.13 
± 0.03 Mg/g (wet weight). 



280 



FIGURE 3 

RELATIONSHIP OF MEAN MERCURY UPTAKE |ng/g| WITH pH 
AND FEEDING REGIME IN RAINBOW TROUT (Salmo gainlneri) 



10 



X 

X 
O;. 



FEEDING 




TREATMENT 


pH 


•— • STARVED 


60 


A—* FED 


7.0 


■"• STARVED 


7.0 


O— O FED 


60 




24 



43 72 

TIME. (Hours:' 



9 b 



i2B 



TABLE 3 



METHYLMERCURY203 CONCENTRATIONS IN RAINBOW TROUT (ng/g) 
AT VARIOUS WALLEYE FEEDING TIMES (hours) and pH TREATMENTS 



Replicate Fish 



Rl 



48h 



pH 5.0* 
72h 96h Sums 



pH 6.0 
48h 72h 96h 



pH 7.0 
Sums 48h 



72h 



96h 



Sums 



3.04 5.58 6.33 14.95 4.46 5.91 7.42 17.79 12.87 1.08 5.73 19.68 
3.72 3.78 5.70 13.20 3.01 2.92 1.31 9.24 10.04 11.99 11.21 33.24 
3.33 4.61 4.82 12.76 4.29 5.01 - 9.30 8.14 7.42 7.56 23.12 



R2 



3.76 


5.79 


8.87 


18.42 


4.84 


5.69 


10.47 


4.54 


5.96 


17.34 


27.84 


3.61 


4.89 


5.51 


3.18 


4.87 


3.42 


11.47 


12.23 


3.17 


17.45 



21.00 


11.21 


2.13 


2.38 


15.72 


14.01 


1.51 


3.29 


3.34 


8.14 


32.85 


3.91 


1.34 


3.39 


8.64 



R3 



4.54 


6.55 


8.34 


19.43 


4.81 


7.40 


4.24 


16.45 


4.91 


4.90 


5.46 


15.27 



2.70 


3.96 


5.47 


6.28 


4.16 


6.84 


4.23 


4.92 


- 



12.13 


10.51 


8.37 


28.75 


47.63 


12.28 


9.41 


15.45 


10.95 


35.81 


9.15 


5.70 


30.56 


13.29 


49.55 



Means 



16.64 



15.86 



26.84 



NOTE: 



Mean values 16.64 and 15.86 ng/g methylmercury^**^ were average ( 



16.64 + 15.86 



= 16.25 ) and represent the total 



amount of methylmercury^*^^ accumulated by rainbow trout at pH 6.0. 

Trout were actually exposed to methylmercury^^^ at pH 6.0, then fed to pH 5.0 walleye. 






TABLE 4 
METHVLMERCURY203 ^ptakE IN FED AND STARVED RAINBOW TROUT 



Concentrations Over Time (ng/g) 

72h 96h 120h 



Feeding 

Regime 


pH 


^4n 
















Starved 

n = 3 


6.0 


0.52 
0.77 
0.50 


(0. 


.60) 


1.06 

1.74 (1.29) 

1.06 


1.41 

2.06 (1. 
1.39 


62) 


1.73 

2.52 (1.96) 

1.63 


1.91 

2.66 (2.15) 
1.87 


Starved 

n = 3 


7.0 


0.90 
1.36 
1.42 


(1 


.23) 


2.13 

1.81 (3.16) 

5.54 


2.95 
2.54 (4 

7.41 


.30) 


3.83 

2-92 (4.83) 

7.75 


4.67 

3.26 (5.38) 

8.22 


Fed 


6.0 


-„ 






4.46 
3.01 


5.91 
2.92 




7.42 
1.31 


- 












4.29 


5.01 




~ 








- 






4.84 

3.61 (5.07) 


5.69 
4.89 (4 


-51) 


10.47 
5.51 (7.78) 


- 


n - 9 










12.23 


3.17 




17.45 














2.70 


3.96 




5.47 














6.28 


4.16 




6.84 








- 






4.23 


4.92 




mortality 




Fed 


7.0 


- 






12.87 
10.04 


1.08 
11.99 




5.73 
11.21 


- 












8.14 


7.42 




7.56 








- 






11.21 
1.51 (8.14) 


2.13 

3.29 (9.07) 


2.38 

3.34 (9.62) 


- 


n = 9 










3.91 


1.34 




3.39 














10.51 


8.37 




28.75 














9.41 


15.45 




10.95 


~ 






- 






5.70 


30.56 




13.29 





ro 
00 



TABLE 5 

METHYLMERCURY^"-^ CONCENTRATIONS IN WALLEYE (ng/g) 
AFTER 120 HOURS EXPOSURE 

Feeding pH 5.0 pH 6.0 pH 7.0 

Regime obs . means obs . means obs . means 



1.12 




1.47 


H = 1.39 


1.59 


C = 0.99 


1.15 


S = 0.87 


0.99 


c = 1.08 


0.83 




0.74 




0.93 




0.94 





m 1.00 1-01 1.02 

H2 0.79 H = 0.85 0.61 H = 0.67 0.89 H = 0.97 

H3 t.77 C = 0.36 0.38 C = 0.69 0.99 C = 0.48 

Rl CI 0.33 S = 0.27 0.72 S = 0.65 0.38 S = 0.50 

C2 0.38 £ = 0.49 0.65 £ = 0.68 0.48 e = 0.65 

C3. 0.36 0.69 0.57 

SI 0.27 0.61 0.58 

82 0.27 0.72 0.48 

,S3 0.28 0.62 0.44 



HI 1.34 1.13 1.82 

H2 1.08 1.18 1.75 

H3 0.82 H = 1.08 1.41 H = 1.24 1.51 H = 1.69 

R2 CI 0.65 C = 0.63 0.81 C ^ 0.75 1.14 C = 1.08 

C2 0.63 S = 0.54 0.66 S = 0.60 1.02 S = 0.76 

C3 0.60 e = 0.75 0.78 £ = 0.86 1.07 £ = 1.18 

51 0.55 0.81 

52 0.52 0.81 

53 0.54 0.66 

HI 2.31 1.12 1.29 

H2 2.06 H = 2.18 1.47 H = 1.39 1.22 H = 1.22 

H3 2.17 C = 0-73 1.59 C = 0.99 1.14 C = 0.70 

CI 0.70 S = 0.67 1.15 S = 0.87 0.68 S = 0.58 

R3 C2 0.59 e = 1.19 0.99 I = 1.08 0.63 £ = 0.83 



C3 0.91 0.83 0.79 

51 0.75 0.74 0.66 

52 0.64 0.93 0.52 

53 0.61 0.94 0.56 

■ ■ [^ 

Overall means from feeding regardless of pH. w 

"Hot fed" =1.26 
"Cold fed" = 0.71 
"Starved" = 0.60 



TABLE 6 

METHYLMERCURY^^^ UPTAKE BY WALLEYE FROM METHYLMERCURY^^^ EXPOSED RAINBOW TROUT 

(ng/g) 



pH 



Replicate 
No. 



Walleye 



Rainbow 
Trout 



Percent Retained 
by Walleye 



Percent Eliminated 
by Walleye 



5.0 



1.00 
0.79 
0.77 
1-34 
1.08 
0.82 
2.31 
2.06 
2.17 



14.95 
16.75 
12.76 
18.42 
27.84 
11.47 
19.43 
16.45 
15.27 



7.0 

5.0 

6.0 

7.0 

4.0 

7.0 

12.0 

13.0 

14.0 

Mean =8.33 



93.0 
95.0 
94.0 
93.0 
96.0 
93.0 
88.0 
87.0 
86.0 
Mean = 91.67 



6.0 



1.07 
0.61 
0.38 
1.13 
1.18 
1.41 
1.12 
1,47 
1.59 



17.79 

7.24 

9.30 

21.00 

14.01 

32.85 

12.13 

17.28 

9.15 



Mean = 



6.0 
8.0 
5.0 
5.0 
8.0 
4.0 
9.0 
9.0 
17.0 
7.88 



Mean = 



94.0 
92.0 
95.0 
95.0 
92.0 
96.0 
91.0 
91.0 
83.0 
92.11 



7.0 



1.02 
0.89 
0.99 
1.82 
1.75 
1.51 
1.29 
1.22 
1.14 



19.68 
32.24 
23.12 
15.72 
8.14 
8.64 
47.63 
35.81 
49.55 



5.0 

3.0 

4.0 

12.0 

21.0 

17.0 

3.0 

3.0 

2.0 

Mean = 7.78 



95.0 
97.0 
96.0 
88.0 
79.0 
83.0 
97.0 
97.0 
98.0 
Mean = 92.22 



00 



285 



Autoradiography 

Methylmercury^*^-^ is apparently taken up by phytoplankton as is shown in 
Figure 4. In this autoradiogram a track emission is evident in an 
individual phytoplankton from pH 5.0 at the 3 o'clock position. Phy- 
toplankton in other pH regimes also appear to incorporate methyl- 
mercury^*^^. Although methylmercury^'^^ is taken up by some algae, others 
show no evidence of track emissions or overlying silver grains (Figure 
5). This specimen was exposed to 4 ng/L methylmercury^^^ for 24 hours 
at pH 7.0. 

Direct counting of Daphnia magna for methylmercury^^^ showed that the 
isotope was accumulated by the animals at pH 6.0 and 7.0 with those of 
the latter regime exhibiting a greater concentration. Processed auto- 
radiograms, however, failed to show any localization of silver grains 
overlying histological sections of the same Daphnia magna specimens. 



286 




FIGURE 4 



ONE PHYTOPLANKTER WITH ONE TRACK EMISSION AND 
A FEW OVERLYING SILVER GRAINS AFTER 24 HOUR EXPOSURE 
TO 4 ng/L METHYLMERCURY ^°^ AT pH 5.0. 
MAGNIFICATION, 635x, 



287 




FIGURE 5 



A NON-RADIOACTIVE PHYTOPLANKTER AS EVIDENCED 
BY THE LACK OF SILVER GRAINS AND TRACK EMISSIONS 
AFTER 24 HOURS EXPOSURE TO 4 ng/L METHYLMERCURY^^^ 
AT pH 7,0. MAGNIFICATION. 367x, 



288 



DISCUSSION 

Study Lakes 

The selected study lakes (Atkins, Walker and Wood) are all found in the 
Muskoka region of Ontario. Although these lakes are not considered to 
be under acid-stress at the present time they display similar physical 
and chemical parameters as lakes that may be affected by acid precipi- 
tation. Total dissolved solids in these lakes varied from 20-30 mg/L and 
are comparable with the range of values (10-49 mg/L) for lakes in the La 
Cloche Mountains of Ontario which are undergoing acidification (Beamish 
and Harvey, 1972; Beamish, 1974; Beamish et al. , 1975). The range of 
hardness values (5.50 to 7.75 mg/L as CaCOs) for the three study lakes 
was slightly lower than the range (7.92 to 16.30 mg/L as CaCO^) for 
lakes in the La Cloche Mountains. The pH ranges of Atkins, Walker and 
Wood (5.30 to 7.20; 6.50 to 6.75; 5.90 to 6.80; respectively) were, 
however, higher than the average of 4.6 for lakes within the La Cloche 
Mountains taken in 1971 (Beamish and Harvey, 1972). 

The three study lakes at present appear to be oligotrophic. If acidic 
inputs continue, it is anticipated these lakes will become increasingly 
oligotrophic , similar to those in the La Cloche Mountains . The poor 
buffering capacity of the lakes is evidenced by the relatively small 
amounts of acid or base required for titration to the pH levels employed 
in this study. The three lakes selected for use in this study are, 
ostensibly, free from heavy metal contamination, as concentrations of 
certain heavy metals (cadmium, copper, lead, mercury and zinc) are all 
within the ranges reported for natural freshwater aquatic environments 
(EPA, 1976; Atchison et al. , 1977; Enk and Mathis , 1977). Generally, 
these concentrations were lower than those observed in acid- stressed 
lakes from similar geographical locations in Ontario (Beamish, 1974) . 

Acid Toxicity to Daphhia 

Mortality rates of Daphnia magna increased markedly with a depression of 
pH. D^ magna appears to be one of the more sensitive species in the 
genus as D^ pulex were observed to tolerate a pH as low as 4.3 (Davis 
and Ozburn, 1969) . The latter species, however, could not reproduce 
successfully below pH 7.0. The protective effect of food on the toxi- 
city of pH in D^ magna is not understood. 

Mercury Levels and Uptake in Experimental Animals 

Mercury content in the trout and walleye used for these experiments was 
very low. The range of concentrations in trout and walleye was from 
0.002 to 0.012 |jg/g and from 0.003 to 0.016 ^g/q respectively, on a wet 
weight basis. These levels are well below the level of 5 pg/g which is 
recommended as being safe for human consumption (EPA, 1976; Reeder et 
al., 1979;). 

Background concentrations of mercury from trout and walleye used in this 
study are representative of uncontaminated specimens. These levels 
correspond to amounts observed in uncontaminated fish from various 
aquatic environments (Aronson et al. , 1976; Abernathy and Cumbie, 1977; 
Brown and Chow, 1977; Lloyd et al. , 1977). Although only three trout and 
two walleye were used for analysis, it is presumed that similar low 



289 



levels of mercury were also present in the other fish comprising the 
stocks used for the experiment. 

Assays for mercury content were not performed for Daphnia magna nor 
Chlorella vulgaris or the indigenous phytoplankton communities of the 
study lakes. Cultures of D. magna and C^ vulgaris were assumed to con- 
tain very low levels of mercury as they were raised in relatively ster- 
ile laboratory conditions. It is unlikely that indigenous phytoplankton 
of the study lakes were contaminated with mercury in view of the rela- 
tively low background levels of the metal in the lake water. 

Estimates of algal biomass or primary productivity by measurement of 
chlorophyll a content indicated a trend toward lower mean values with 
increasing acidity. These observations were, however, not statistically 
significant (ANOVA, P <0.05). An apparent decrease in primary produc- 
tivity as well as a reduction in the diversity of phytoplankton com- 
munities has been reported as a result of increased acidity (Kwiatkowski 
and Roff, 1976). Yan et al. , (1977) suggest, however, that algal bio- 
mass does not significantly decrease in acid lakes. Although insignifi- 
cant, the trends observed in this study contradict the suggestion of Yan 
et al. (1977). More precisely designed laboratory experiments may 
provide further insight into the ultimate elucidation of the problem. 

Daphnia magna could not be cultured at pH values lower than 7.0. This 
observation is consistent with that reported for D^ pulex , a species 
which also cannot reproduce at pH 5.0 and 6.0 (Davis and Ozburn, 1969). 
Both species, however, can tolerate pH levels below those of neutrality. 

Methylmercury2t»3 uptake by D^ magna was monitored at pH 6.0 and 7.0. 
Uptake data are, however, not available at pH 5.0 as this acid regime 
was shown to be lethal to the experimental animals. After 24 hour 
exposure to methylmercury203^ significant accumulations of the compound 
had taken place. Daphnia exposed to methylmercury^^^ g^ pH 7.0 accumu- 
lated approximately 1.7 times as much methylmercury^o^ compared with 
Daphnia at pH 6.0. Huckabee et al. (1975) and Lock (1975) also reported 
that Daphnia sg. accumulate Hg very rapidly. The differences between the 
content of Daphnia at pH 6 .0 and 7 .0 after 24 hours may not relate to 
the levels accumulated after longer term exposures since the eguilibrium 
concentration of methylmercury is usually not acquired until after 6 
days of exposure to the metal (Huckabee et al. , 1975). Differences in 
uptake between Daphnia at the two pH exposures may, however, be related 
to metabolic rate, feeding behaviour or some other factor. Daphnia at 
neutral pH would probably be respiring and feeding at rates typical of 
healthy individuals. Exposure to the lower pH treatment (pH = 6.0) may 
have caused an alteration of respiration rate or feeding behaviour which 
may have ultimately affected the amount of methylmercury^^s being ac- 
cumulated. One could perceive, for example, that acid exposure might 
depress appetite in Daphnia thus precluding methylmercury 203 accumula- 
tion to the same extent or greater as normally feeding individuals. 

There were a few apparent erroneous estimates of methylmercury^os con- 
centration in the ecosystem columns but these measurements could not 
have explained the differences in the quantity of methylmercury^^^ in 
Daphnia exposed to the metal at pH 6.0 and 7.0. The accumulation of Hg 
by Daphnia as a function of pH should be investigated more thoroughly as 



290 



it may be affecting metabolic rate, feeding behaviour, excretion, or a 
number of other life processes. 

Although direct measurements of methylmercury^*^^ in Daphnia magna showed 
the isotope was readily taken up, autoradiographs failed to show any 
localization of silver grains that could be attributed to the isotope . 
In this study, Kodak NTB3 nuclear emulsion was used to detect the lo- 
calization of the CH3 Hg^^^ as atoms of Hg^*^^. It would appear that 
NTB3 nuclear emulsion would be adequate for localization of Hg^'^^ as the 
emulsion can record p particles at minimum ionization (Rogers , 1973) . 
Rogers (1973) indicates, for example, that Kodak NTB3 nuclear emission 
will record p particles of any energy including those at minimum ioniza- 
tion. This would include, of course, Hg^*^^ which has a p particle 
emission at 0.20 MeV. The lack of silver grains in the Daphnia auto- 
radiographs may be related to development time . The specific activity 
of the Hg^*^'^ label in the Daphnia may have required longer periods of 
development than the time regimes used in the current study. 

Track autoradiography of Hg^*^^ in phytoplankton clearly indicated that 
methylmercury^*^^ was incorporated by algae. Phytoplankton autoradio- 
graphs employed a thicker emulsion layer compared with those for 
Daphnia . In track autoradiographs , the passage of a beta particle is 
recorded as a string of silver grains as shown in Figure 4. Not all 
phytoplankton, however, exhibited track emissions (Figure 5) . The ap- 
parent absence of the isotope from certain algae may suggest that par- 
ticular species have a greater affinity for the element or that inherent 
species differences are reflective of differential accumulation factors. 

Methylmercury^**^ uptake by rainbow trout was greater in fed fish exposed 
to the isotope at pH 7.0 compared with fish at pH 6.0. Trout accumu- 
lated significantly more methylmercury^*^^ at pH 7 . than 6.0. Walleye 
feeding on the former group were obviously presented with greater total 
amounts of methylmercury in their diet. The relative importance of food 
and diet on methylmercury uptake in trout is apparent from perusal of 
Figure 3. Approximately 2 to 3 times more methylmercury^*^"^ was accumu- 
lated by fish that were fed at both pH 6.0 and 7.0 compared with starved 
fish Comparisons of methylmercury^'^-'^ content in "fed" and "starved" 
trout indicated that 70.6% and 44.1% of the total amount of methyl- 
mercury^'^''^ accumulated by trout at pH 6.0 and 7.0, respectively, was due 
to ingestion. The latter estimation of food's contribution to total 
mercury levels agrees well with observations from other studies 
(Hannerz, 1968; Huckabee et al. , 1975; Norstrom et al. , 1976; Phillips 
and Buhler, 1978). A figure of 44.1% for trout at pH 7.0 is interesting 
and may suggest that uptake via water is more significant at higher pH. 
It may not be coincidence, therefore, that trends toward lower methyl- 
mercury^^"^ levels were observed at pH 7 . compared with columns at 
pH 5.0 and 6.0. In a study with inorganic mercury, Tsai et al. (1975) 
found, however, that the uptake of mercury by fathead minnows increased 
sharply at pH values below 7.0. They interpreted their observations as 
being due to the formation of less reactive mercury hydroxide complexes 
at the higher pH regimes. In the current study, the mercury was in the 
form of methylmercury and, hence, the formation of hydroxide complexes 
at more alkaline pH regimes was likely precluded. The uptake dynamics 
of inorganic mercury cannot, therefore, be compared to those of methyl- 
mercury at similar pH levels. 



291 



The mechanism by which pH effects mercury uptake by fish is not clear. 
It is suggested that an unidentified metabolic parameter is contributing 
to the enhanced uptake of methylmercury^'^^ at pH levels near neutrality. 
This parameter may be related to reduced elimination rates and/or in- 
creased uptake of the isotope from the food or water. 

Under field conditions, fish in acid-stressed environments have exhi- 
bited enhanced tissue levels of methylmercury {Landner and Larsson, 
1972, Suns et al. , 1980). Intuitively, one would have expected to 
verify such observations experimentally but the results of this study 
have yielded data contrary to this hypothesis. 

Miller and Akagi (1979) have shown that the enhanced uptake of methyl- 
mercury by fish in acid-stressed environments is related to increased 
levels of the compound rather than a physiological response of the 
animals. They found, for example, that changing values of the pH in 
natural sediment -water systems did not affect the total amount of 
methylmercury generated in the sediments. They also observed that the 
partition of methylmercury between water and sediment did change with 
the amount of methylmercury in the water column; doubling for a decrease 
in pH of 1 or 2 units depending on sediment type. Miller and Akagi 
(1979) also indicated that these changes were enough to quantitatively 
explain the observed elevations in fish taken from lakes of low pH. 

In the present study, rainbow trout were exposed to similar levels of 
methylmercury^*^*^ at three different pH regimes. As there was no sedi- 
ment component in the simulated ecosystem columns the concentrations of 
methylmercury^"^ did not change in the water as a result of sediment 
methylation or repartitioning. Elucidation of the effects of methyl- 
mercury uptake by fish in low pH environments is somewhat confused by 
the results of this study in comparison with recent theories on the 
subject. 

Unlike rainbow trout, walleye did not accumulate methylmercury^'^^ dif- 
ferently with pH. Starvation did not affect the amount of methyl- 
mercury203 taken up from water, as walleye fed with unlabelled trout 
displayed a similar quantity of accumulated mercury. Walleye that were 
fed with methylmercury^^^ exposed trout accumulated roughly twice as 
much methylmercury^'^^ ^g ngtarved" or "cold-fed" walleye. The contri- 
bution of methylmercury2 03 from food in walleye fed with methyl- 
mercury203 „as roughly 50%. Jernelov (1970) reported similar data which 
suggested that 50% of the mercury in Swedish pike came directly from the 
water. These data do not contribute to the elucidation of the hypo- 
thesis that food is the greatest contributor to body-burden levels of 
mercury in exposed fish. 

The relative percentage contribution of methylmercury^^^ by food ob- 
served for walleye in this study may have been underestimated. 
Methylmercury203 contaminated trout were exposed to the isotope for a 
maximum of 4 days prior to predation by walleye. This period of ex- 
posure may not have been adequate for methylmercury^*^-'' to reach an 
equilibrium in trout. Overall body burden levels in these fish may, 
therefore, have been lower compared with trout exposed to similar levels 
of methylmercury^"^ for prolonged periods under natural conditions. For 
this reason, the ultimate levels of methylmercury203 contributed by the 
trout may not have been as large if the trout had been exposed to the 
radioisotope for longer periods. 



292 



The percent of methylmercury^^^ retained or eliminated in walleye did 
not differ with pH and ranged from 7.78 to 8.33 percent and from 91.67 
to 92.22 percent respectively. These retention data are somewhat less 
than the 41.6% figure observed for trout by Hamelink et al. (1975). In 
their study, however, the retention values represented data from fish 
that had been exposed to methylmercury for one year. Mercury uptake for 
walleye in this study may not have reached equilibrium in the relatively 
short exposure period of 4 days. The estimates presented for retention 
and elimination of methylmercury^^^ may, therefore, be erroneous. 
Huckabee et al. (1975) found for example, that the elimination of methyl- 
mercury^ ^^~ from mosquito fish ( Gambusia af finis ) was greatest in the 
fish 5 days after feeding, dropping off to a relatively constant elimi- 
nation rate after 20 days. 

The maximum levels of mercury reported in walleye after the experiment 
were all well below the Environment Canada (Reeder et al. 1979) safe 
level of 0.5 |jg/g. Final whole body concentrations on a wet weight basis 
ranged from 0.11 to 0.13 \^q/q. Acidity did not affect the concentration 
of mercury in experimental fish nor did the feeding treatments. Concen- 
trations of mercury in post experimental walleye were, however, about an 
order of magnitude higher compared with walleye that were analysed prior 
to the beginning of the experiments. This increase cannot be explained 
by the mercury accumulated from exposure to methylmercury^^-^ since the 
walleye accumulated the isotope in less than 3 ng/g quantities at all pH 
treatments. An addition of 3 ng/g of mercury to pre-experimental mer- 
cury levels would be difficult to detect. 

The data presented in this report show methylmercury' s potential for 
movement and accumulation at various trophic levels of the aquatic 
ecosystem. Fish and zooplankton exposed to neutral pH regimes accumu- 
late more methylmercury compared with animals exposed at more acid pH. 

In the natural environment, however, the concentration of methylmercury 
is higher in acid-stressed fish. One must conclude that there are other 
factors contributing to the accumulation of methylmercury in these 
organisms, besides acidity. Water quality as well as mercury- 
methylation rates and concentrations, for example, are probably affect- 
ing the accumulation of the compound by fish in acid waters. Additional 
studies are required to increase the understanding of the dynamics of 
methylmercury uptake in fish especially from acid environments. 



293 



REFERENCES 

Abernathy, A.R. and P.M. Cumbie . 1977. Mercury accumulation by large- 
mouth bass ( Micropterus salmoides ) in recently impounded reser- 
voirs. Bull. Env. Contamin. and Toxicol. 17(5) : 595-600. 

Aronson, J.L., M. Spiesman and A.K. Aronson. 1976. Note on the distri- 
bution of mercury in fish species in three Ohio Lakes. Environ. 
Pollut. 10:1-7. 

Atchison, G.J., B.R. Murphy, W.E. Bishop, A.W. Mcintosh and R.A. Mayer. 
1977. Trace metal contamination of bluegill ( Lepomis macrochirus) 
from two Indiana Lakes. Trans. Am. Fish, Soc. 106:637-640. 

Beamish, R.J. and H.H. Harvey. 1972. Acidification of the La Cloche 
Mountain lakes, Ontario and resulting fish mortalities J. Fish. 
Res. Bd. Canada 29: 1131-1143. 

Beamish , R.J. 1974 . Loss of fish populations from unexploited remote 
lakes in Ontario, Canada as a consequence of atmospheric fallout of 
acid. Water Rec. 8:85-95. 

Beamish, R.J., W.L. Lockhart, J.C. Van Loon and H.H. Harvey. 1975. 
Long-term acidification of a lake and resulting effects on fishes. 
Ambio. 4:98-102. 

Brown, J.R. and L.Y. Chow. 1977. Heavy metal concentrations in Ontario 
fish. Bull. Env. Contamin. Toxicol. 17(25): 190-195. 

Carter, J.C.H. 1971. Distribution and abundance of planktonic Crusta- 
cean in ponds near Georgian Bay (Ontario, Canada) in relation to 
hydrography and water chemistry. Arch. Hydrobid. 68:204-231. 

Craig, G.R. and W.F. Baksi. 1977. The effects of depressed pH on 
flagfish reproduction, growth and survival. Water Res. 11 : 621-626. 

Davis, P. and S.W. Ozburn. 1969. The pH tolerance of Daphnia pulex 
(Leydig, emed. , Richard). Can. J. Zool. 47:1173-1175. 

Dillon, P.J., D.S. Jeffries, W. Snyder, R. Reid, N.D. Yan, D. Evans, J. 
Moss and W.A. Schneider. 1977. Acidic precipitation in south- 
central Ontario: recent observations. Ont. Min. Environment. 

Enk, M.D. and B.J. Mathis. 1977. Distribution of cadmium and lead in a 
stream ecosystem. Hydrobiologia 52(2-3): 153-158. 

EPA. 1976. Quality Criteria for Water . U.S. Environmental Protection 
Agency. EPA-440/9-76-023 . 

Hamelink J., R.C. Waybrant and P.R. Yant . 1975. Mechanisms of bio- 
accumulation of mercury and chlorinated hydrocarbons and pesticides 
by fish in lentic and lotic ecosystems, pp. 262-281. In; Fate of 
Pollutants in the Air and Water Environments - Part 2. Chemical 
and Biological Fate of Pollutants in the Environment. Vol. 8. I.H. 
Suffet (ed.). 



294 



Manners, L. 1968. Experimental investigations on the accumulation of 
mercury in the water organisms. Inst. Freshwater Res. Drottning- 
holm 48: 120-176. 

Harvey, H.H. 1975. Fish populations in a large group of acid-stressed 
lakes. Verh. Internat. Verein. Limnol. 19:2406-2417. 

Harvey , H.H. Personal communication . University of Toronto , Toronto , 
Ontario. 

Hodson, P.V. and E.S. Millard. 1977. Experimental ecosystems as a means 
of evaluating the fate and effect of contaminants in aquatic eco- 
systems. In: Proceedings of the 4th Annual Toxicity Workshop, 
Vancouver, B.C., November 1977. Fish. Mar. Serv. Tech. Report. 

Huckabee, J.W., R.A. Goldstein, S.A. Janzen and S.E. Woock. 1975. 
Methylmercury in a freshwater food chain, p. 199-215. International 
Conferences on Heavy Metals in the Environment Symposium Proceed- 
ings Vol . II , Part I , October 27-31 , 1975 . Toronto , Ontario , 
Canada. 

Humason, G. 1972. Animal Tissue Techniques . W.H. Freeman and Company, 
San Francisco. 641 pp. 

Jernelov, A. and H. Lann. 1971. Mercury accumulation in food chains. 
Oikos 22:403-406. 

Johansson, N., J,E. Kihlstrom and A. Walberg. 1973. Low pH values shown 
to affect developing fish eggs (Brachydavine cecis , Hasn-Buch) . 
Ambio 2:1-2. 

Knoechel, R. and J. Kalff. 1976a. The applicability of grain density 
autoradiography to the quantitative determination of algal species 
production: A critique. Limnol. Oceanogr . 21(4) : 583-590 . 

Knoechel, R. and J. Kalff. 1976b. Track autoradiography: A method for 
the determination of phytoplankton species productivity. Limnol, 
Oceanogr. 21(4): 590-596. 

Krenkel, P. A. 1974. Mercury: environmental considerations. Part II. 
Chemical Rubber Co. Crit. Review Environ. Control 4(3) : 251-339. 

Kwiatkowski, R.E. and J.C. Roff. 1976. Effects of acidity on the 
phytoplankton and primary productivity of selected northern Ontario 
lakes. Can. J. Botany 54(22); 2546-2561. 

Landner, L. and P.O. Larsson. 1972. IVL Report B115-Swedish Institute 
for Water and Air Pollution Research, Stockholm. (In Swedish) . 

Leivestad, H. and I. P. Muniz . 1976. Fish kill at low pH in a Norwegian 
River. Nature 259:391-392. 

Leivestad, H., G. Hendrey, I. P. Muniz and E. Snekvik. 1976. Effects of 
acid precipitation on freshwater organisms, pp. 87-111. In: F.H. 
Braekke (ed.). Impact of acid precipitation on forest and fresh- 
water ecosystems in Norway. Research Report 6. Agricultural 
Research Council of Norway, Norwegian Council for Scientific and 
Industrial Research. 



295 



Likens, G.E., R.F. Wright, J.N. Galloway and T.J. Butler. 1979. Acid 
rain. Scientific American 241(4): 43-52. 

Lloyd, E.T., W.T. Schnemk and J.O. Stoffer. 1977. Mercury accumulation 
in trout of southern Missouri. Environ. Res. 13:62-73. 

Lock, R.A.C. 1975. Uptake of methylmercury by aquatic organisms from 
water and food. Sublethal effects of toxic chemicals on aquatic 
animals. Proc. Swedish-Netherlands Symp. J.H. Koeman and J.J. 
T.W.A. Stik (eds.) pp. 61-79. 

Menendez, R. 1976. Chronic effects of reduced pH on brook trout. J. 
Fish. Res. Bd. Canada 33:118-123. 

Miller, D.R. and H. Akagi. 1979. pH affects mercury distribution not 
methylation. Ecotoxicology and Environmental Safety 3:36-38. 

Mount, D.I. 1973. Chronic effect of low pH on fathead minnow survival, 
growth and reproduction. Water Res. 7:987-993. 

Norstrom, R.J. and M. Brounstein. 1974. Chemical analysis, 1972-1973. 
Report A, pp. 19A1-19A50. In: Distribution and Transport of Resis- 
tent Chemicals in Flowing Water Ecosystems. D.R. Miller (ed.). 
Report No . 2 , Ottawa River Proj ec t . Div . Biol . Sci . Natl . Res . 
Counc . Car . Ottawa , Ontario . 

Norstrom, R.J., A.E. McKinnon and A.S.W. de Freitas. 1976. A bioener- 
getic model for pollutant accumulation by fish- Simulation of PCB 
and methylmercury residue levels in Ottawa yellow perch ( Perc'a 
flavescens) . J. Fish Res. Bd. Canada 33(2) ;248-267 . 

Phillips, G.R. and D.R. Buhler. 1978. The relative contributions of 
methylmercury from food or water to rainbow trout ( Salmo gairdneri ) 
in a controlled laboratory environment . Trans . Am. Fish Soc . 
107(6):853-861. 

Phillips, G.R. and R.C. Russo. 1978. Metal bioaccumulation in fishes 
and aquatic invertebrates: A literature review. EPA-600/3-78-103. 

Rand, M.C. , A.E. Greenberg, M.J. Taras and M.A. Franson. 1976. Standard 
Methods . American Public Health Association, American Water Works 
Association, Water Pollution Control Federation. 1193 pp. 

Reeder, S.W., A. Demayo and M.C. Taylor. 1979. Mercury. In: Guide- 
lines for Surface Water Quality. Vol . I . Inorganic Chemical Sub- 
stances. Environment Canada. Inland Waters Directorate, Water 
Quality Branch. 16pp. 

Rodgers, D. Personal Communication. University of Guelph, Guelph, 
Ontario. 

Rof f , J . C . and R . E . Kwiatkowski . 1977 . Zooplankton and zoobenthos 
communities of selected northern Ontario lakes of different acidi- 
ties. Can. J. 2ool. 55:899-911. 



296 



Rogers, A.W. 1973. Techniques of Autoradiography . Elsevier, Amsterdam, 
London, New York. 372p. 

Ryan, P.M. and H.H. Harvey. 1979. Growth reponses of yellow perch, 
Perca f lavescens (Mitchell), to lake acidification in the La Cloche 
Mountain Lakes of Ontario. Unpublished manuscript. 

Salazkin , A . A . 1971 . Zooplankton in oligotrophic lakes of the humid 
zone in the northwestern USSR. Gibrobiol. Zh. 7:23-28. 

Scheider, w., I. Adamski and M. Paylor. 1975. Reclamation of acidified 
lakes near Sudbury, Ontario. Ontario Ministry of the Environment. 
129 p. 

Schindler, D.W. 1979. Acid rain. A lecture presented at British 
Columbia Hydro and Power Authority , Vancouver , B.C. November 1 3 , 
1979. 

Schofield, C.L. 1976. Effects of acid precipitation on fish. Presented 
at International Conference on the Effects of the Acid Precipita- 
tion. Telemark, Norway. June 14-19, 1976. 20pp. 

Sprague, J.B. 1973. The ABC's of pollutant bioassay using fish, pp. 
6-30. In: Biological Methods for the Assessment of Water Quality . 
ASTM, STP 528. American Society for Testing and Materials. 256 pp. 

Sprules, W.G. 1975. Midsummer crustacean zooplankton communities in 
acid-stressed lakes. J. Fish. Res - Bd- Canada 32:389-395. 

Suns, K. 1978. Personal communication. Liminology and Toxicity Section. 
Ministry of the Environment, Ontario. 

Suns, K., C. Curry and D. Russell. 1980. The effect of water quality 
and morphometric parameters on mercury uptake by yearling yellow 
perch ( Perca f lavescens ) . Technical Report L.T.S. 80-1. 

Tsai, S.C., G.M- Boush and F. Matsumura. 1975. Importance of water pH 
in accumulation of inorganic mercury in fish. Bull. Env. Contam. 
Toxicol. 13(2): 188-193. 

Yan, N.D. W.A. Schneider and P.J. Dillon. 1977. Chemical and biological 
changes in Nelson Lake, Ontario following experimental elevation of 
lake pH. Proc. 12th Canadian Symposium 1977: Water Pollution 
Research Canada. 



297 



ATMOSPHERIC DEPOSITION OF MERCURY IN ONTARIO 

BY 

S.C. BARTON. N.D. JOHNSON AND J. CFRISTISON 

ONTARIO RESEARCH FOUNDATION 

SHERIDAN PARK RESEARCH COMMUNITY 

MISSISSAUGA, ONTARIO 

AND 

S. GEWURTZ* 

ONTARIO MINISTRY OF THE ENVIRONMENT 
880 BAY STREET 
TORONTO, ONTARIO 

PRESENTED AT 

ONTARIO MINISTRY OF THE ENVIRONMENT 
TECHNOLOGY TRANSFER CONFERENCE NO. 1 
SKYLINE HOTEL 
NOVEMBER 25, 1980 



* Present Affiliation: Ministry of Labour 

400 University Avenue 
Toronto , Ontario 



298 



ABSTRACT 

The cause of elevated mercury levels in fish of freshwater lakes 
remote from known sources in Ontario and elsewhere has yet to be identified. 
The importance of atmospheric transport of mercury from remote sources to 
land and water surfaces in Ontario has been investigated in this study. Im- 
proved sampling and analytical methodology for the measurement of mercury 
in air and precipitation have been developed and a field study was conducted 
for six months which included both a suburban and remote site. Continuous 
and cumulative sampling techniques were used simultaneously to measure air- 
borne mercury levels and the relative importance of elemental, organic and 
particulate components was assessed. Conventional wet deposition sampling 
techniques were modified to enable proper compensation for mercury vapour 

uptake by preservative solutions. Prevailing ambient concentrations were 

-3 
generally consistent with earlier studies (1 to 10 ng.m ) with elemental 

mercury being the main constituent. Particulate mercury accounted for less 
than 15% of the total mercury and organomercury vapour was essentially non- 
detectable. Directional patterns showed little evidence of a predominant 

long range transport mechanism for airborne mercury. Wet deposition was found 

-2 —1 
to make a considerably more important contribution ('^ 20 to 30 yg.m year ) 

than dry particulate deposition whereas preliminary vertical profile measure- 
ments indicated that dry vapour deposition may be of major importance. Based 

on the experimental results, the total flux of mercury to the land surface in 

-2 -1 
Ontario is in the range of 75 to 140 ug.m year and thus similar to con- 
tinental deposition rates assumed in recent global mercury budgets. 



299 
INTRODUCTION 

The occurrence of elevated mercury levels in fish of freshwater 
lakes remote from known sources in Ontario, and elsewhere, is still not fully 
understood. The objective of this study was to obtain experimental data which 
would help to define the possible role of the atmosphere as a medium for the 
transfer of mercury to land and water surfaces remote from known sources. 

Environmental concern about mercury appears to have commenced as 
early as 1700 when a citizen of an Italian town sought an injunction against a 
factory making mercuric chloride because It's fumes apparently were killing 
people in the town. However, current environmental concern about mercury is 
based largely on experiences of the past two decades, and has arisen primarily 
from the acute toxic effects which have occurred amongst people eating fish and 
seed grain contaminated with mercury compounds (1). Much has been written on 
these incidents and, in Canada, the subject has received attention since the 
late 1960's when rivers and lakes in Ontario were closed to fishing because of 
mercury pollution. In the early incidences contamination could generally be 
traced to some local industrial source, but as the investigations continued, 
mercury was found to exist in numerous organisms and the environment in general, 
with significant amounts being found in areas quite remote from any known sources, 
Rivers in Northern Ontario, and lakes in the Muskoka district of Ontario, the 
Adirondacks in New York State and Southern New Brunswick were specific areas of 
concern. 

Natural processes irtiich have been releasing mercury to the environ- 
ment for billions of years include the weathering of mercury-containing mineral 
formations, soil degassing and volcanic emanations, and to a lesser extent, 
emissions from land biota (Table 1). Major anthroprogenic sources from which 
mercury can be emitted into the atmosphere include the combustion of fossil 
fuels, sulphide ore smelting, cement production, the Chlor-Alkali process, in- 
cineration and numerous other uses. As a result of these many and diverse uses, 
in conjunction with the numerous natural sources, mercury is an ubiquitous 
element found throughout the environment in its various chemical forms. 

Global mercury cycles have been derived in recent years in an attempt 
to provide at least a semi-quantitative assessment of the relative importance of 



300 

iiatural and anthropogenic sources and to define the relative importance 
of the various pathways and sinks (2, 3). It is now generally accepted 
that the atmosphere can be an important transport medium for mercury, with 
a currently estimated residence time of only 11 days, compared to thousands 
of years for other compartments of the environment. However, relatively 
little direct experimental evidence is available regarding the transport and 
deposition mechanisms whereby mercury is removed from the atmosphere and 
transferred to land and water surfaces. 

OBJECTIVES OF STUDY 

The attainment of a better understanding of the atmospheric trans- 
port and subsequent deposition of mercury on land and water surfaces in 
Ontario was the overall objective of this study. Specific objectives were: 

• to collect experimental data on the atmospheric levels and 
deposition rates of mercury 

• to define deposition flux to land and water surfaces in 
specific urban and rural areas of Ontario 

• to characterize predominant transport and deposition 
mechanisms and species 

Specific phases of the study were: 

• literature review to collect all relevant information 

• development of sampling and analytical methodology to 
quantitatively define both airborne concentrations and 
deposition rates of particulate and vapour mercury 

• assembly of a field monitoring facility 

• six-naDnth field survey at two sites 

• assessment of the experimental data. 

The ubiquitous occurrence of low levels of mercury throughout the 
environment provides a special challenge in attempting to quantitate atmospheric 
levels. The development and evaluation of appropriate methods, both sampling 
and analytical, was an essential and important component of the study, and the 



301 



details of this phase of the work are described elsewhere (4). 

EXPERIMENTAL METHODS 

Field studies were initiated in February 1979 in Sheridan Park, 
and continued in the Dorset area until mid-August. The studies at Sheridan 
Park were designed primarily to field test the equipment and methods but 
also to provide information on mercury levels and characteristics in an urban 
area. The Dorset site was selected as being representative of the Muskoka 
area. The monitoring and sample collection activities undertaken can be sum- 
marized as follows: 

• -measurement of atmospheric levels of elemental, particulate 

and organic mercury, with both continuous and cumulative 
measuring techniques 

• measurement of mercury content of both wet and dry 
deposition samples on both a "routine" and "event" basis 

• measurement of dry vapour deposition by velocity profile 
measurements 

• measurement of meteorological parameters such as wind direction 
and speed, rainfall, humidity, temperature and pressure. 

The field equipment used to achieve these measurements is shown 
schematically on Figure 1 and consisted of: 

• Scintrex continuous mercury monitor 

• cumulative 24-hour sampling train capable of differentiating 
between particulate, elemental and organomercury compounds, 
based upon amalgamation of mercury with silver. Organomercury 
compounds pyrolyzed prior to collection on one side of parallel 
collectors 

calibration equipment for static mercury vapour injection 
high-volume sampler 

cascade impactor used occasionally on high-volume sampler 
automatic wet/dry deposition sampler and conventional bulk sampler 
meteorological equipment including wind direction and speed, 
barograph, hygrothermograph and rain/snow gauge. 



302 

The system was designed for unattended operation for periods of 
several days. Wet, dry and total deposition samples were collected in nitric 
acid/potassium dichromate preservative solutions (5) and extensive blank pro- 
cedures were instituted to make allowance for the uptake of mercury vapour by 
the acidic solutions and for other possible sources of contamination. Pre- 
cipitation samples were collected on both a weekly and event basis. 

All samples were analyzed by cold vapour atomic absorption spectro- 
photometry after appropriate sample extraction and digestion procedures. 

DISCUSSION OF RESULTS 

Predominant Species 

Mercury emissions from anthropogenic sources are known to be pre- 
dominantly in the elemental form, whereas natural sources involving biological 
processes are believed to give rise to organomercury compounds. The principal 
classes of mercury generally considered to occur in the atmosphere are (6) : 

• elemental mercury vapour 

• mercury chloride vapour and other volatile salts 

• various species adsorbed on particulate matter 

• organomercury compounds such as methyl and dimethylmercury. 

The monitoring techniques utilized in this study were designed to 
quantitatively define the relative importance of elemental mercury vapour, 
total organomercury (vapour) compounds, and total particulate mercury. The 
overall results indicate the following proportions of elemental, organic and 
particulate mercury: 

y^ OF TOTAL 
CLASS 
Elemental 
Organic (vapour) 
Total particulate 

Thus, the results quantitatively confirm the predominance of elemental 
mercury in the atmosphere and the observed percentages of other components 
also are in general agreement with earlier studies. A statistical evaluation 
of the data lead to the conclusion that the calculated difference between 



SUBURBAN 


REMOTE 


84 


89 


4 


3 


12 


8 



303 

"total" and "elemental" measurements (equal to the organomercury compound) 
was not significant at the 95% confidence level. This, and other features 
of Che data, indicate that organomercury species do not play an important 
role in atmospheric transport and deposition processes. 

Frevailing Ambient Levels and General Features 

Airborne mercury concentrations have been reported to depend on 
the geographical locations, meteorological conditions, altitude, season of 
Che year and time of day. Unfortunately, conflicting reports exist in many 

instances. The range of mercury concentrations usually cited for unpolluted 

-3 -3 

air is 1-10 ng.m , whereas levels from less than 1 ng.m in remote areas to 

-3 
tens of thousands of ng.m near point sources are reported (7). The levels 

measured in this study are summarized in Table 2. The predominance of 

elemental mercury is apparent and the levels at the remote site were consistently 

lower than in the urban area. At Dorset, all hourly values were below 20 ng.m"^, 

whereas a considerably larger range (up to '\' 200 ng.m ) was observed at Che 

urban site. The measured 24-hour levels are in good agreement with the results 

of earlier studies which are summarized in Table 3 (8). 

The potential influence of meteorological parameters on mercury levels 
has been discussed in the literature. Inspection of the data (primarily in the 
form of diurnal profiles) showed no apparent correlation at eiCher site of am- 
bient mercury levels with parameters such as temperature, relative humidity, 
barometric pressure or wind speed. However, correlation of elemental mercury 
levels with wind direction showed patterns of considerable int'erest, as shown 
in Figure 2. At Sheridan Park, higher than average mercury concentrations 
correlated quite strongly with Easterly winds. Specific features of the results 
that indicate the higher mercury concentrations from Easterly Directions were 
the result of local point sources rather than long-range transport are: 

• fairly abrupt changes in mercury concentration-time profiles 
in conjunction with wind shifts, and 

• rapidly fluctuating mercury levels (five-fold increases typically 
occurred within a few minutes) rather than high continuous levels 
during the events. 



304 



The observed high levels from NE - E directions could be the 
results of emissions from several sources: 

• Sheridan Park laboratory and Pilot Plant facilities (to the ENE - E) 

• The Lakeview generating station (to the ENE) 

• The Toronto/Mississauga urban plume (N - NE sector). 

The highly structured concentration-time profiles and, to a lesser 
extent, the relatively low levels from N and NNE directions indicate that a 
diffuse urban plume was not the predominant source of mercury at this site. 
The highest levels from easterly directions are consistent with the presence 
of the very local potential sources mentioned above. The NE contribution could 
be attributed to either local emissions or the Lakeview generating station. 

Wind frequency distributions for the survey period are also shown in 
Figure 2 and must be taken into account in assessing directional distributions 
expressed as average concentrations. Directional distributions of total dosages 
(concentration X time) for each wind direction were also calculated. This 
directional profile is considerably different from that based upon average con- 
centrations, and the relative magnitudes for each direction are very similar to 
the wind frequency pattern. Thus, despite the observation of occasional periods 
of relatively high mercury levels associated with winds from the direction of 
potential sources, it must be concluded that there is really no predominant source 
contributing to average mercury levels at this suburban location. 

The Dorset data are presented in a similar fashion in Figure 3. Con- 
sistently low mercury levels in this area (overall mean concentration = 3 ng.m ) 
were determined by both sampling techniques. As already discussed, the minimal 
daily variation about the mean and lack of events were other important features 
of the data. No significant directional distribution of average concentrations 
was found for either the hourly or daily measurements. As shown by the wind 
frequency distribution, winds from the SE quadrant occurred only a small portion 
of the time and thus measurements under these conditions were very infrequent. 
A directional distribution of mercury dosage also was calculated for the Dorset 
site and is virtually identical to the wind frequency distribution. This, and ' 
other features of the data, demonstrates the lack of any specific, predominant 
long-range transport mechanism which contributes to ambient mercury levels in 
the Dorset area. 



305 



Deposition MeasuremenCs 

Concern with the fate of atmospheric pollutants and their potential 
impact on the aquatic and terrestrial environment has resulted in an increased 
interest in removal processes in recent years. An important component of this 
study has been the experimental determination of the mercury flux to land and 
water surfaces which can be expected to occur in Ontario, 

Atmospheric deposition processes whereby pollutants can be removed 
from the atmosphere are many and complex, but can be arbitrarily divided into 
two categories, wet and dry, and each category can in turn be subdivided with 
respect to the removal of gases and particulates. Wet processes include rainout 
from clouds, washout under clouds and chemical transformations between aerosols 
and water droplets. 

Dry deposition is the direct transfer of material from the atmosphere 
to the earth* s surface. Processes affecting dry deposition of a pollutant In- 
clude gravitational settling, transport by atmospheric turbulence, impaction, 
heterogeneous and homogeneous reactions, concurrent surface fluxes, and ad- 
sorption and absorption processes of both atmospheric aerosols and various 
constituents on the receptor surface. Simple conceptual definitions of the wet 
and dry deposition processes have been used to evaluate the experimental results 
obtained in this study (9) . 

Total, wet and dry particulate deposition samples were collected on 
both a weekly and event basis, using preservative solution to trap and stabilize 
the mercury constituents. Blanks were exposed to compensate for vapour uptake 

by the solution. An automated Sangamo sampler was used to collect wet samples. 
An attempt was also made to measure directly dry deposition, using the other 
side of the sampler, and a "bulk" or total deposition was also collected in an 
open beaker. After defining methods and conducting limited studies at Sheridan 

Park, a total of "^ 11 weekly samples and 8 events were collected at the Dorset 

-2 -1 
site. The mean wet deposition rate was 0.4 yg.m wk (or event) with in- 

-2 -1 
dividual values ranging from ND to 0.8 ug.m wk . The average mercury concen- 
tration in precipitation was 0.02 ppb. The results are summarized in 
Table 4 in terms of annual loadings. 



306 



Important features of the wet deposition results are: 

• only minor variations occurred in mercury concentrations, and 
so variations in deposition flux depended primarily on quantity 
of precipitation 

» slightly higher concentrations were usually obtained in event 
than in weekly sampling, but this may be due to a larger par- 
ticulate contribution to the event samples 

• average amounts of rainfall fell during the survey period on 
both a seasonal and yearly basis 

• The results are in good agreement with earlier precipitation 
(snow) studies conducted in Quebec and Ontario (10). 

Considerable disagreement exists as to the efficiency of precipitation 
in washing out relatively insoluble mercury vapours (11, 12). The continuous 
mercury measurements made during rainstorms permitted a direct assessment of 
this effect. The concentration profiles during precipitation events did not 
show clear evidence of an effective washout mechanism which either increased or 
reduced mercury levels. In any event, both washout coefficient and scavenging 
ratio calculations (9) were made for comparison with the experimental results. 
The scavenging ratio results, shown in Table 4 gave the better agreement with 
the experimental results. 

The directly measured dry particulate deposition component of the 
total mercury flux was non-detectable at Dorset (Table 4). The somewhat higher 
contribution determined from the difference between the total and wet collections 

is believed to be less accurate than the direct measurements because of 
inadequacies in the blank corrections that were available for this sampling 
mode. The calculated dry deposition flux values were determined using mass 
median particulate diameters measured at the Dorset site by cascade im- 
paction methods. The average measured particulate mercury concentrations, 
and corresponding deposition velocities of 0.25 and 0.07 cm. sec for grass 
(Dorset) and a smooth surface (snow, Sheridan Park) (9) , respectively. The 
calculated values are higher than, but of the same magnitude as, the measured 
rates, confirming their basic validity. 



307 



As discussed above, the direcc absorption of a gas at a surface can 
be an important mechanism for the removal of pollutants from the atmosphere. 
Dry vapour deposition velocities for mercury have not been measured experimen- 
tally to any significant extent. Estimates in the range of 0.1 to 1.0 cm. sec 
have been made and a value of 0.3 cm. sec has been advocated as a suitable 
estimate for general use (13). For comparison, a typical value for SO^ is 
1 cm. sec 

Vertical profile measurements of pollutant concentrations and rele- 
vant meteorological parameters can be used to estimate the dry vapour flux 
occurring under a given set of conditions (lA). A limited number of such 
measurements were made at the Dorset site and the concentration and wind profiles 
are shown in Figure 4. The lowest sampling point was just above the canopy of 
tall grass and weeds in the vicinity of the site. Several features of the data 
can be noted : 

• an unexpected minimum in the mercury concentration profile 
appears to occur at - 1.4 ra with the effect being more predominant 
under daytime conditions. If this minimum is ignored and treated 
simply as scatter in the data, a slight increase in concentration 
with height is observed, suggesting a relatively small net trans- 
fer to the surface 

• The fetch of uniform surface upward of the site was at least 
100 times the sampling height 

• wind speed profiles show an essentially exponential increase 
with height 

• neutral to moderately unstable conditions prevailed during 
the study period 

• ambient mercury levels were quite constant during the study 
period. 



308 



The mean mercury and wind profiles have been used in conjunction 
with the mass transfer coefficient approach (14) to estimate a deposition flux 
as follows: 

F " C .U, (X -X ) 
p z z o 

where C = 1.35 x lO""^ 
P 

and 2, the reference height, was taken to be 10 m. 
The day and night profiles were then used to determine the following deposition 
velocity and flux ranges: 

V = 0.06 to 0.1 cm.sec' 
g 

-2 -1 
Flux = 45 to 110 ng.m year 

These estimates are slightly lower than the deposition velocities that have 
been previously assumed. However, the values are very similar to those that 
can be derived from Hogstrom' s (15) recent study of mercury levels and deposition 
rates near a point source which is the most quantitative and recent assessment 
of mercury transport and deposition currently available. On the basis of these 
results and the estimates made using Hogstrom' s modelling work, it is concluded 
that the dry vapour mercury deposition velocity is somewhat lower than previously 
assumed, and a range of 0.06 - 0.1 cm. sec seems probable at this time. This 

range, in conjunction with prevailing ambient concentrations at the Dorset site, 

-2 -1 
indicates a dry vapour deposition flux of approximately 45 to 110 yg.m year , 

and consequently it is the most significant component of the total deposition 
flux. 



SUMMARY AND CONCLUSIONS 

The results have been used to quantify the major features of a simple 
model for the atmospheric transport and deposition of mercury (Figure 5) and 
the results can be summarized as follows: 



309 



-3 
Ambient levels of - 10 ng.m total mercury were found in 

-3 
Mlssissauga, in comparison with ==3.5 ng.m in the Dorset 

area. The higher levels in Sheridan Park are attributable 
to specific anthropogenic emissions. 

Elemental mercury vapour was the major component in each area, 
organomercury vapour was not a significant fraction, and par- 
ticulate mercury levels were less than 15% of the total mercury. 
Greater than 50% of particulate mercury occurred in the fine 
particulate fractions (< 2.2 ym) . These results are in good 
agreement with average concentrations reported in other studies 
for similar urban and remote areas in North America. 
No strong diurnal variation in mercury concentrations was observed 
at either station and there was no apparent correlation with 
meteorological parameters (i.e. temperature, barometric pressure, 
relative humidity and wind speed), which were measured concur- 
rently. Unlike mercury, these parameters in most cases showed 
quite distinct and consistent diurnal variations. 
Correlations of mercury concentrations with wind direction in- 
dicated a local source or sources of predominantly elemental 
mercury vapour East to Northeast of the Sheridan Park sampling 
station, consistent with known potential sources* Apart from the 
few higher levels obtained from the Easterly direction, the mercury 
input to the area was practically independent of wind direction 
and was proportional to the wind frequency distribution. The same 
conclusion holds true for the results at Dorset where low levels 
(2-6 ng.m ) occurred with winds from any direction. Thus, no 
marked influence of long-range transport from any predominant area 

or point source is evident at either sampling station. 

-2 
A mean wet deposition flux value of approximately 20 - 30 ug.m 

year~ occurred at both sampling areas, although slightly higher 

mercury concentration In precipitation were found at Sheridan Park 

in comparison with the values at Dorset, 0.02 and 0,04 ppb, 

respectively. 



310 



• Dry particulate deposition accounted for a relatively minor 
proportion of the total deposition flux at the suburban station 

where the directly measured annual flux was found to be 

-2 -1 
= 5 yg.m year . At Dorset the contribution by dry particulate 

deposition was essentially non-detectable. 

• On the basis of limited vertical profile measurements, net dry 

vapour deposition was estimated to be approximately 45 to 110 

-2 -1 
yg.m year at Dorset and is thus a major fraction of the total 

deposition flux. Although this is the least well quantified 

aspect of the total deposition flux, the estimated dry vapour 

deposition velocities (0.06 - 0.1 cm. sec ), compare favourably 

with the value of 0.08 cm. sec estimated from the results of a 

recent study near a point source. 

• The total deposition flux to land and water surfaces in Ontario 

-2 -1 
was estimated to be 75 to 140 yg.m year and dry vapour depo- 
sition, which appears to be the most important component, is 
least well-defined. 

In conclusion, elemental mercury vapour is the predominant atmospheric 
constituent, and levels found in Ontario are consistent with the results of studies 
in other areas. Directional patterns and other features of the data show little 
evidence of a predominant long-range transport mechanism. The estimated total 
deposition flux in Ontario appears to be similar to continental deposition rates 
postulated in recent global mercury budgets. .The consolidation and integration 
of the results of this study with those of other on-going aquatic and terrestrial 
effects studies should be pursued in order to provide a thorough understanding of 
the mobilization of mercury in the environment. 



311 



REFERENCES 



1. L.J. Goldwater, Mercury in the Environment, Scientific American 
224 (5), 1971. 

2. National Academy of Sciences, An Assessment of Mercury in the Environment, 
Washington, B.C., 1978 . 

3. E.L, Kothny, The Three-Phase Equilibrium of Mercury in Nature, Trace 
Elements in the Environment, Advances in Chemistry Series No. 123, American 
Chemical Society, 1973. 

4. S.C. Barton, N.D. Johnson and J. Christison, A Study of Atmospheric Mercury 
Deposition in Ontario, ORE Report P-2699/G-04 to the Ontario Ministry of 
the Environment, January, 1980. 

5. Environment Canada, Atmospheric Mercury Deposition Workshop, Canada Centre 
for Inland Waters, Burlington, Ontario, May 1979. 

6. Batelle Columbus Laboratories, Multimedia Levels - Mercury, Report prepared 
for the U.S. Environmental Protection Agency, NTIS PB 273 201, September 1977, 

7. I.e. Sherbin, Mercury in the Canadian Environment, Volumes I and II, Report 
prepared by the Environmental Protection Service, Fisheries and Environment 
Canada, EPS 3- EC-79-6, April 1979. 

8. W.H. Van Horn, Materials Balance and Technology Assessment of Mercury and 
its Compounds on National and Regional Basis, U.S. Environmental Protection 
Agency, NTIS PB 247 000, 1975. 

9. P.J. Denison, J. A. McMahon and J.R. Kramer, Literature Review on Pollution 
Deposition Processes, Project ME 3-6 for Alberta Oil Sands, Environmental 
Research Program and Syncrude Canada Limited, February 1979. 

10. R.J. P. Brouzes, M.O. Farkas , R.A.N. McLean, S.R. McGraw, and G.H. Tomlinson, 
Measurement and Effects of Atmospheric Input of Mercury to Lakes, Paper 
presented before the Division of Environmental Chemistry, American Chemical 
Society, Washington, September 1979. 

11. H.B. Cooper Jr., G.D. Rawlings and R.S. Foote, Measurement of Mercury Vapour 
Concentrations in Urban Atmospheres, Instrumental Society of America Trans. 
13 (4), 1974. 



I 



312 



12. D.J. Johnson and R.S. Braman, Distribution of Atmospheric Mercury 
Species Near Ground, Environmental Science and Technology 8^, 1975. 

13. P.J. Barry, An Introduction to the Exposure Commitment Concept with 
Reference to Environmental Mercury, Monitoring and Assessment Research 
Centre Technical Report No. 12, 1979. 

14. Bunsel Environmental Consultants, Particulate and Gaseous Dry Deposition 
from the Atmosphere to the Earth's Surface, Draft Report for Ontario Ministry 
of the Environment, August 1978. 

15. U. Hogstrom et al, A Study of Atmospheric Mercury Dispersion, Atmospheric 
Environment 13 (A), 1979. 



313 



TABLE 1 



SOURCES OF MERCURY 



NATURAL 



- WEATHERING OF MERCURY-CONTAINING MINERAL FORMATIONS 

- SOIL DEGASSING 

- OCEANIC E>aSSIONS 

- VOLCANIC EMISSIONS 

- ORGANIC VAPOURS AND PARTICLES FROM LAND BIOTA 



ANTHROPOGENIC 



- COMBUSTION OF FOSSIL FUELS 

- SULPHIDE ORE SMELTING 

- CEMENT PRODUCTION 

- CHLOR-ALKALI PROCESS 

- INCINERATION OF MERCURY- CONTAINING ARTICLES 

- NUMEROUS AND VARIED INDUSTRIAL USES INCLUDING ~ AGRICLT.TURE, 
LABORATORIES, DENTAL, ELECTRICAL APPARATUS, ETC. 



TABLE 2 



SUMMARY OF MERCURY CONCENTRATIONS 



314 



SAKPLE TYPE 



ELEMENTAL 



AVERAGE DAILY MEANS (ng.n"^) 
SUBURBAN REMOTE 



8.2 



3.3 



PARTICULATE 



1.2 



0.3 



ORGANIC 
TOTAL 



9.7 



'uO.l 
3.6 



315 



TABLE 3 



Summary of Current Data on Atmospheric Mercury Levels for 
Various Locations 

(Van Horn, I975) 
Range Mean 



(ng/ 



m' 



A. Remote and Rural Areas 



\ Fig/ 11" 

and Rural Areas 

Oceanic 

Particulate < 0.005-0. 06 <0.15 

Vapor 0.6-0.7 0.7 

Non-mi nera 1 i zed terrestrial 

Particulate < 0.005-1.9 0.15 

Vapor 1-10 k.O 

Volcan i c 

Particulate + vapor 20-37,000 

Mineral! zed terrestrial 

Particulate + vapor 7-20,000 - 

B. Urban Areas 

Particulate < 0.01-220 2,h 

Vapor 0.5-50 7-0 

C. I ndus trial ■'■ 

Vapor 7-5,000,000 



■''■These measurements include chlor-alkali plants, thermometer factories, 
smelters and mercury mi-nes. 



TABLE 4 



TOTAL, mj AND DRY PARTICULATE FLUX 



WET 



1 



316 



DRY 



TOM, MEAS. CALC. BY DIFF. DIRECT CALC 



SHERIDAJI PARK 31 23 



32 



26 



DORSET 



32 



21 



23 



11 



ND 



24 



^^gur^^- ^^•MOIgygRK^gdCU^^ON^QRING^UT 



TOTAL WET-DRY DEPOSITION 

DEPOSITION RAIN-SNOW SAMPLER 

SAMPLER GAUGE SAMHLtH 



<3==<Z1 



HYGROTHERMOGRAPH 



n 



CONTROL UNIT 

a 

POWER SUPPLY 



SAMPLE CELL 



FILTER 
M UNIT 



BAROGRAPH 



RAIN -SNOW 

GAUGE 
RECORDER 



SCINTREX 
RECORDER 



VANE 
ANEMOMETER 
RECORDER 



/ _\ 




[ 



HIGH 
VOLUME 
SAMPLER 




SAMPLE 
INLET 




CUMULATIVE \ 

SAMPLER 



NUTECH 
SAMPLER 



NUTECH 
SAMPLER 




METEOROLOGICAL 
TOWER 






318 



Figure 2 - directional distributioms at sherdda.'* park 




5 10 nq.m 
'■■■•' 1 



r3 



A DIRECTIONAL DISTRIBUTTOS OF HOinaY - 
AVERAGE MERCURY CO:{CENTRATIONS 




C_ DIRECTIONAL DISTRIBUTIOIi OF 
KERCORY DOSAGE 



10% 
I 



N 




^ VEm3 frequency DISTRISUItON 



5 10% 
ti I r. I I 



319 



Figure 3 - dirzctiosal distribution at dors^t 



H 




nq-m 



■3 



A DIXZCTIO.SAL DISTRIBUTION OF P.0LTCY-AVE5AC- 

HEaCUSY CCNCE1.T?ATI0N5 




n 



C DIR£CTI0«AL DISTXIBimON OF 
MBiani? DOSAGE 




10% 



B Vl^ID FREqUEJCY DtSTRIBinilON 



10% 

_l 



320 



Figure 4 -VERTICAL PROFILE SAMPLING AT DORSET 
(12-HOUR AVERAGE DETERMINATIONS) 



DAY 



6.0 - 

5.0 

4.0 
3.0 
2.0 
1.0 

7.5 

6.0 

4.5 
3.0 

1.5 




0.7 1.4 2 



NIGHT 




"8.4 " 0.7 1.4 2 
HEIGHT ABOVE GROUND (m> 



874 



Figure 5 -SUMMARY OF DEPOSITION KATF.S AND MAJOR PATHWAYS OF AIRIJORNE MKRCURY TO LAND 

AND WATER SURFACES IN THE llAMBURTON AREA 



Dispersion 



SOURCE 
background 



Dispersion 



> 



PARTICULATE M/VTTER 

-3 
0.3 ng.m (<10% of total airborne 

mercury) 

-(tOT, oC mercury content asnoc Lntetl with 

pnrtlcles of _<2 .0 v'ln dlameLor 



Adsorption (not well defined) 



3.0 ng . ni 



-3 



VAPOUR 

(~ 90% elemental mercury, 
< 3% organomercury) 



Net Dry Vapour Depoi;lLion 
(A5-110 iig.ir^.yr"^) 



^ 



> 



± 



RAIN 

Wet Scavenging of 
Particulate and Vapoui 
" 0.02 ppb 



Wet Deposition 
(a 20 pg.m"^.yr"^) 




Dry Particulate Deposition 
(non-detectable) 



* Real-time measurements during precipitation events did not indicate any pronounced washout affect 



4jj 



322 



EVENT PRECIPITATION SAMPLERS 

FOR USE IN 

ACID RAIN STUDIES 



by 

D. M. KANE 

UNITED TECHNOLOGY and SCIENCE INC 
75 Eglinton Avenue East 
Toronto, Ontario M4P 1H3 



Presented at the 

TECHNOLOGY TRANSFER CONFERENCE NO. 1 
Skyline Hotel, Toronto, Ontario 
November 28, 1980 



323 



TABLE OF CONTENTS 



ACKNOWLEDGEMENTS 



INTRODUCTION 



FIELD STUDY 



RESULTS AND DISCUSSION t 



CONCLUSIONS 11 



REFERENCES It 



ACKNOWLEDGEMENTS 



I would like to acknowledge the efforts of Dr. Sam Stevens of Concord 
Scientific Corp., who conceived, designed and assessed the results of 
the study; Mrs. Margot Brideau for the extensive statistical analysis 
and Ms. Francis Widmar for the chemical analysis. I would also like to 
thank the Ontario Ministry of the Environment for sponsoring this study 
which was financed through the Provincial Lottery Trust Fund. 



LIST OF FIGURES 



FIGURE 1: SCHEMATIC DIAGRAM OF WOODBRIDGE AES 
EXPERIMENTAL STATION 



324 



FIGURE 2: SAMPLER ARRANGEMENT 



FIGURE 3: TABLE OF BETWEEN SAMPLER VARIATION 



FIGURE 4: RATIOS OF H CONCENTRATION 



FIGURE 5: RAINFALL RECOVERY RATIOS 



FIGURE 6: AEROCHEM METRICS SAMPLER CORRELATION 
COEFFICIENT MATRIX - ALL EVENTS 



6 
9 

n 

n 

13 



FIGURE 7: AEROCHEM METRICS SAMPLER CORRELATION 
COEFFICIENT MATRIX - 
LOW CONTAMINATION INDEX (<n ) 



15 



FIGURE 8: AEROCHEM METRICS SAMPLER CORRELATION 
COEFFICIENT MATRIX - 
HIGH CONTAMINATION INDEX {>n) 



16 



■ 7 w^^ -»<.■ 



r-4 ,-- - , - . , 



^1 ^r~ i.."i •■■•! 



325 



INTRODUCTION 



up until relatively recently, the sampling of precipitation for chemical 
analysis was thought to be a fairly simple matter and consequently it 
was common for fairly simple approaches to be used. These included a 
variety of designs of open containers, constructed of a number of materials, 
and these were left out at the sampling sites for varying periods, typically 
the order of a month. In the early 1970's, a number of investigators 
became concerned about this type of approach and several studies were 
conducted (1-5) to compare the performance of different precipitation 
sampler designs and sampling methodologies. These studies have yielded 
a number of important conclusions of which the following are relevant to 
the work described here: 

• The ratio of monthly bulk deposition to monthly wet deposition 
is significantly greater than 1.0 for several parameters 

• Results from composite samples for sampling periods greater than 
one week can be very different from those obtained by summing 
amounts in individual storm samples over the same periods 

• The Hubbard-Brook (funnel and plastic bottle) and the Health and 
Safety Lab. (HASL) have been found to be the most satisfactory 
samplers 

• All of the automatic samplers perform unsatisfactorily during 
rain - freezing rain - snow episodes 



The time of storage of samplers should be minimized 



326 



• Wind shields do not consistently improve the collection efficiency 
of a precipitation sampler relative to a standard rain gauge 

• Evaporation can be a serious problem 

• Automatic samplers have poor snow collection efficiency 

■ For snow collection, the sampler height to diameter ratio is an 
important factor in collection efficiency 

• Standard rain and snow gauges are necessary to determine the 
precipitation quantity. 

The data available to date indicates that an automatic wet only type 
sampler operated in an event mode would satisfactorily minimize the dry 
deposition and other contaminant contributions to a collected rain sample, 
and thus provide reliable data upon which meaningful interpretations could 
be made. However, the relatively high cost (2-5K capital, several hundred 
dollars installation and maintenance costs) makes the use of this type of 
sampler for an event network of any appreciable size somewhat unattractive 
financially. Thus, if a satisfactory, inexpensive alternative could be 
found, it would represent a significant step forward in event precipitation 
sampling. 

Designs which have been used for inexpensive precipitation sampling include 
the M.O.E. "Sudbury Environmental Study Event" sampler. This is a simple 
device consisting of a large mouth plastic bucket lined with a polyethylene 
bag. The polyethylene bag has been modified so as to form a funnel shape 
at the collection surface thus minimizing contamination. However, because 
of the wide mouth of the collection, and the fact that it is open for a 
full 24 hour period with the possibility of dry periods in this interval, 
the possibility of a sample contamination is greater than for automatic 
samplers. 



327 



Another design that has sometimes been used is the "funnel and bottle" 
design. This sampler uses a large plastic funnel to collect precipitation 
which is drained into a bottle. This design affords a relatively large 
collection area while at the same time offering a relatively small area 
for dry deposition or other contamination. 

To assist in the selection of a satisfactory sampler, a comparative study 
of the three types of samplers, described above, was carried out for the 
Ontario Ministry of the Environment. The samplers were operated for 24 
hours for each event and the study ran from mid-August to the end of 
November 1979. 



328 



FIELD STUDY 



The site for this investigation was the Atmospheric Environment Service's 
Experimental Station at Woodbridge, Ontario. A rough map showing the 
study site location is given in Figure 1. This site was well equipped 
having, in addition to the equipment used for this study, a variety of 
instruments including: a Fisher-Porter rain gauge; Tipping Bucket Rain 
gauge; 2 x 10m meteorological towers with anemometers; 2 Sangamo 
automatic rain samplers, one operated by the M.O.E. and the other by 
CCIW; 2 CCIW bulk samplers and a M.O.E. storage gauge. 

The sampling instruments used in this study were two Aerochem Metrics 
automatic event samplers, designated as A in the study; two funnel and 
bottle samplers, designated F; and two Sudbury Environment Study events 
samplers, designated S. Also, two strip chart recorders installed in a 
covered box were used to record the open/close cycle of the automatic 
samplers. The actual sampler arrangement is illustrated in Figure 2. 

The sampling procedure is as follows: 

At approximately 0830 hours, an assessment by MEP Company meteorologists 
was made of the probability of precipitation occuring that day. If the 
probability was greater than 25%, then carefully cleaned (de-ionized H^O 
washed) sample containers were transported to the site in clean plastic 
bags and installed in the samplers. The installation was usually complete 
by 0930 hours. The san^les were picked up at 0930 hours the following day, 
and, if rain was forecast for that day as well, a new set of containers 
was installed in the rain samplers. The collected samples were transported 
immediately to the laboratory and the pH and sample volume were determined 



- 1 km 



Service Road 



Study Collectors 



A 



-e- 16 m 



I 



-.1 




f 






-3 

m 

r+ 

~i 

fD 



Various Instruments 

2 10 m met towers 

1 ARBlSangamo 

1 CCIWj 

2 CCIW Bulk Samples 
1 Nipher Gauge 



Hwy. 7 



FIGURE 1: SCHEMATIC DIAGRAM OF WOODBRIOGE AES EXPERIMENTAL STATION 






330 



FIGURE 2: SAMPLER ARRANGEMENT 



/ 



^^ 



/ 



O 



o 



Q Aerochem Metrics Collector 

gl Funnel and Bottle Collector 

A Sudbury Environmental Study Event Collector 



331 



as soon as possible (typically h hour) after pick-up. The samples were 
then stored in polyethylene bottles at approximately 4°C until analysis. 
The storage time before analysis varied from one week to about two months. 

Analysis was carried out usually from 1 week to about 2 months after 
collection: In all. 32 events were sampled over the period of the study. 

Analysis of the samples was carried out for pH, sulphate, nitrate, bromide, 
chloride, fluoride, sulphite, nitrite, phosphate, sodium, potassium, 
magnesium, calcium and ammonium ions and conductivity. Except for pH 
and conductivity, all analyses were carried out using ion chromatography. 
It was found that concentrations of bromide, sulphite, nitrite and phosphate 
were so low that they were totally masked by the presence of much more 
dominant ions (e.g. sulphate and nitrate) in the chromatogram, and thus 
these ions are subsequently not considered. 

A laboratory intercomparison study of analytical methods was carried out 
with the Water Quality Section of the Laboratories Branch of the OME. 
No significant difference between results from the two labs were found. 



332 



RESULTS AND DISCUSSION 

The concentration data for each parameter measured over the 32 events 
of the study were examined statistically using the "paired t-test" to 
estimate the variance within sampler type and between sampler types. 

The results of the within sampler comparison show that, at a 95% confidence 
level, there is no significant difference between the results obtained by 
two samplers of the same type for any parameter with the exception of 
rainfall amount for the F samplers and HgO"^ with the S sampler. A break- 
down of the data by rainfall amount, which will be discussed later, revealed 
that the significant difference for the F sampler occurred during heavier 
rainfalls, indicating that spillage may be a problem here. The H30-*' 
difference for the S sampler is at present not clear. 

For the between sampler comparison, the F and S samplers were compared to 
the A samplers as it was felt that this sampler type was less prone to 
extraneous contamination and thus gave the "truest" results. Several 
differences were noted, as illustrated for selected parameters in 
Figure 3. Both the F and S samplers showed significant differences 
from the A sampler for a number of soil related parameters such as 
calcium and magnesium as well as for a number of non-soil related 
parameters such as hydrogen ion. sulphate and nitrate. Other parameters 
showing significant differences are potassium and sodium. There were no 
significant differences found between samplers for ammonia, conductivity 
and rainfall amount. The S sampler gave better agreement for all parameters 
with the A sampler as reflected by lower t values. 

The observed differences are almost certainly due to dry contamination. 
The effect of this dry contamination on the H"^ concentration would depend 



333 



FIGURE 3: BETWEEN SAMPLER VARIATION 



COMPARISON 




sV" 


NO3- 


h" 


NH^^ 


Ca^^ 


M 2 + 

Mg 




(1) 


S 


S 


s 


NS 


S 


S 


A vs F 


(2) 


5.11 


4.67 


3.13 


1.94 


4.60 


3.93 




(3) 


26 


26 


26 


26 


26 


27 




(1) 


S 


S 


S 


NS 


S 


S 


A vs S 


(2) 


4.07 


3.75 


2.29 


1.37 


3.80 


3.11 




(3) 


26 


26 


26 


26 


25 


27 



(1) Significant (S) or not significant (NS) at 95% confidence level 

(2) Calculated value of t 

(3) No. of events 



334 



on whether the contaminating compound formed a base or acid in solution. 
Also a compound containing sulphate, such as MgS04 would also affect the 
sulphate concentration. Another source of sulphate contamination would 
be the dry deposition and subsequent oxidation of sulfur dioxide. 

The ratio of hydrogen ion concentration in the F and S samplers compared 
to the hydrogen ion concentration in the A sampler is averaged in Figure 4. 
It can be seen that hydrogen 1on concentration in the F or S sampler is, 
on average, only 88 and 85% respectively of that found in the A sampler, 
however, the standard deviation indicates the considerable variation in 
these figures. 

No significant difference in rainfall recovery was found between the A 
and F and A and S samplers. However, the average rainfall measured by 
the three samplers is different from that measured by the standard tipping 
bucket rain gauge as illustrated in Figure 5. The A sampler results are 
on average close to those obtained with the tipping bucket gauge, differing 
by only 3%. However, there is considerable variation in these results so 
this should only be used as a comparison guide. 

Concentration ratio plots were prepared for each parameter. The ratios 
were found to vary substantially from 1.0, and are particularly bad for 
the soil related elements Ca^"*" and Mg^"*", especially where the observed 
concentrations were near the detection limit for these parameters in the 
A sampler, and thus only a small amount of contamination would be required 
to make the ratio much greater than 1.0. 

Matrices of correlation coefficients between each parameter measured were 
calculated for the three types of sampler for all events. For this study, 
the data obtained for the Aerochem Metrics sampler are probably the best 
representation of the parameters in precipitation of the three samplers 



FIGURE 4: RATIOS OF H"*" CONCENTRATION 



335 



Ratio {H+) 


In Sampler 'X' 




(H+) 


In Aerochem Metrics 






•^av/^v 


Sav/^v 


Average 


0.88 


0.85 


SO 


0.74 


0.56 



FIGURE 5: RAINFALL RECOVERY RATIOS 




336 



tested, as the potential for contamination is the least for this type 
of sampler. The correlation matrix for this sampler is illustrated in 
Figure 6. 

Examination reveals some expected and some surprising results. Some of 

+ 2- 

the expected good correlations found are correlations between H , SO. , 

2+ 2+ + - 

NO^ , between Ca and Mg , Na . CI . Surprising correlations are the 

2+ + 

reasonable correlation between Ca and SO- , and the poor correlation 

+ + 2- - 

between NH- and H , SO^ , NO^ . However, notwithstanding the above 

observations, the correlation matrices for the F and S samplers were 

found to be significantly different from the A sampler, as found in the 

"t-test" comparisons. 

To try and rationalize the results obtained with different samplers, the 
whole data set was divided into subsets. These are; events with rainfall 
greater than or equal to 2.8nin, events with rainfall less than 2,8nfn, 
events where the product of the average wind speed during the dry period 
times the fraction of the sampling period which was dry was less than or 
equal to 11, and similarly for greater than 11. The latter division is 
a form of contamination index. These subsets were chosen to see if any 
relationship existed between: 

a) the quantity of rain and the observed variance within and between 
sampler types 

b) The potential for contamination during dry periods and the observed 
variance within and between sampler types. 

The within and between sampler variations were again examined using the 
paired "t-test". Within sampler variation shows that both the A and F 
samplers showed marginally significant difference in volume collected 
during higher rainfall periods, (i.e. >2.8mm, <11 contamination index). 



FIGURE 6: AEROCHEM METRICS SAMPLER 

CORRELATION COEFFICIENT MATRIX - ALL EVENTS 



NO. 



.64 



SO4-2 



.67 .71 



NH. 



.34 



.58 .50 



CT 



-.05 .35 



.26 



.04 



.01 



.39 .34 



.20 .30 



Cond 
+2 



Ca 



Mg 



Na 



+2 



.93 .86 .92 



.01 



-.12 .21 



.84 .16 .23 



,33 .56 -.06 ,41 



.40 



NO3" SO^"^ NH^"^ CI 



.32 



-.03 .25 .47 -.07 .44 .31 



-.15 .19 .37 -.21 .64 .18 



.44 .23 .25 



.07 






.01 


.94 




-.03 


.56 


.47 


.40 


.54 


.22 


Cond 


Ca^2 


Mq^2 



.32 



Na 






338 



Between sampler variation showed significant differences, particularly for 
the S sampler during events when precipitation was low (<2.8, >11) for the 
parameters, H"*", SO^^", Ca2+, Na"*". K"^, and rainfall amount whereas for high 
precipitation (^.8, <11) no significant differences were observed. This 
indicates the effect of dry deposition during periods of no rain. 

To further illustrate these effects of dry deposition, Figure 7 shows the 
correlation matrix for events where shorter dry periods and lighter winds 
occurred, thus dry contamination is expected to be a minimum. We can see, 
for example, that the NH^"*" vs H"'' correlation has increased from 0.34 to 0.82. 
and the Ca^"*" vs 504^' correlation has decreased from 0.56 to 0.37. Other 
parameters show similar changes. However, as illustrated in Figure 8, for 

events where longer dry periods and higher winds occurred, the NH^'*" vs H 

2+ 
correlation disappears and in fact becomes negative, whereas the Ca vs 

SO42- correlation increases from 0.56 to 0.92. This gives a very clear 

demonstration that dry contamination is occurring. Similar effects are 

seen for other parameters. It should also be noted that these results 

are for the A sampler, the least affected by dry contamination. This 

suggests that this can be a serious problem even for automatic samplers 

and that for these conditions, what is measured is a complex combination 

of precipitation, dry deposition or contamination and evaporation. It 

should be reiterated that these effects are more marked for the F and S 

samplers. 



FIGURE 7: AEROCHEM METRICS SAMPLER 

CORRELATION COEFFICIENT MATRIX - LOW CONTAMINATION INDEX ^11) 



N03" 


-M- 






















SO^-2 


.96 


.76 




















nh/ 


M 


.90 


.84 


















cT 


-.01 


.20 


-.12 


.21 
















F" 


M.. 


.53 


.21 


.23 


-.03 














Cond 


.97 


.89 


.97 


.88 


.12 


.39 












Ca-^2 


M 


.00 


.37 


.11 


-.25 


-.11 


-.08 










Mg"2 


-.16 


-.04 


-.12 


-.02 


-.07 


-.15 


-.16 


.97 








Na^ 


-.17 


-.03 


-.06 


-.18 


.04 


-.15 


.01 


-.10 


-.05 






K^ 


.56 


.42 


.49 


.51 


-.38 


.17 


.54 


-.07 


-.59 


-.41 


; 


Vol 


.13 


-.53 


.07 


-.27 


-.24 


-.39 


-.17 


-.34 


..M 


-.17 


.36 




i 


NO3- 


so^-^ 


NH^^ 


CI" 


F" 


Cond 


Ca^2 


Mg"2 


Na* 


f : 



FIGURE 8: AEROCHEM METRICS SAMPLER 

CORRELATION COEFFICIENT MATRIX - HIGH CONTAMINATION INDEX {>n) 



N03- 


.45 






















S04-2 


.28 


.64 








• 












nh/ 


-.37 


.04 


.08 


















CT 


.08 


.63 


.70 


-.09 
















F" 


-.17 


.13 


.50 


.10 


.58 














Cond 


.77 


.81 


.70 


.76 


.42 


-.06 












Ca^2 


.28 


.71 


.92 


-.18 


.76 


.59 


.58 










Mg^2 


• 5*T 


.61 


.86 


-.18 


.80 


.72 


.58 


.92 








Na^ 


.08 


.50 


.68 


-.25 


.79 


.18 


.40 


.68 


.62 






K* 


-.31 


.34 


.48 


.63 


.30 


.30 


-.24 


.38 


.13 


.22 




Vol 


.00 


-.26 


-.62 


-.23 


-.62 


-.41 


-.46 


-.48 


-.50 


-.52 


-.42 




H^ 


NO3- 


-2 

SO4 


NH^"" 


CI" 


F" 


Cond 


Ca^2 


Mg"2 


Na" 


K^ 



341 



CONCLUSIONS 

The conclusions of the study are: 

• The A sampler performed best of the three tested 

• The F and S type samplers yield significantly different results 
from the A sampler for a number of parameters 

• The S sampler was in better agreement than the F sampler 

• The S sampler was the simplest to use 

• The A sampler has a rain catch efficiency close to the tipping 
bucket rain gauge 

• Differences observed between the results appear to be due to 
dry contamination 

• Division of the data set according to rainfall amount and a contam- 
ination index support the above conclusion 

• Evaporation does not appear to be a problem in 24 hour sampling. 



342 



REFERENCES 

1. R. L. Berry, D, M. Whelpdale, H. A. Wiebe, "An Evaluation of 
Collectors for Precipitation Chemistry Sampling", Presented 
at the WMO Meeting on Wet and Dry Deposition, Atmospheric 
Environment Service, Downsview, Ontario, November 1975. 

2. J. N. Galloway, G. E. Likens, Water, Air and Soil Pollution, 
6, 241 (1976) 

3.. J. N. Galloway, 6. E. Likens, Tellus, 30. 71 (1978) 

4. L. J. Granat, Great Lakes Research, 2(1), 42 (1976) 

5. MAP3S Precipitation Intercomparison Study, MAP3S Progress Report 
for FY1977 and 1978. 



343 



DEFINITION OF THE SPHERE OF INFLUENCE OF THE MINING ACTIVITIES 
AT ELLIOT LAKE. ONTARIO. BY ASSESSMENT OF THE LEVELS OF URANIUM 
AND OTHER ELEMENTS IN LICHENS AND MOSSES 

E. KliiboeM.*, V,H,S. UchoAd^on, L BoU.e,au, P.J. BecfecXt and 

E.V. HaJUbnan 

Faculty oi Sci^nc^ and EngXmzAlng, 
LauAQntian UyiivzM'ity , SudbuAy, Ontofiio 
P3E ZC6 and 

*VzpaJVbr\<mt oi ZlocJi2ml&tAy , McMa6ieA iliUveji&lty , 
Faculty ol Haalth Scxenca^, 1200 Mocn SVitfLt W., 
HamUUon, OntaAA,o LSW 315 



1 . INTRODUCTION 

Lichens and mosses are valuable plants for monitoring the 
environment as they accumulate elements by trapping particulates (tiny 
dust particles) as well as by absorption of dissolved minerals (Nieboer 
et al., 1978). These plants, collectively called cryptogams, do not 
have elaborate root systems. Consequently, uptake from the substratum 
is minimal in most species compared to the accumulation through the plant 
body (called the thallus) by dry deposition of dust and from solids and 
electrolytes in rain and sxirface water (Nieboer et al . , 1978; Svoboda and 
Taylor, 1979). In various parts of the world, lichens and mosses have 
been used to monitor the levels of more than 25 different elements in 
studies of environmental quality around smelters, manufacturing plants, 
and urban centres (e.g.. Rao et al . , 1977; Richardson et al. , 1980; 
Nieboer and Richardson, 1980). However, lichens and mosses have not been 
used specifically for the monitoring of uranium until recently. Selected 
highlights of this new work are described in this report. An assessment 
of the accumulation of uranium and related elements in lichens and mosses 
indicates the feasibility to evaluate the sphere of influence of the 
uranium mining and milling operations in the town of Elliot Lake, Ontario, 



344 
2. EXPERIMENTAL APPROACH 

Lichen and moss samples were collected along a 54 km SSE macro- 
transect originating near the Elliot Lake mining and milling centres (Fig.l) 
Separate collections were also made along micro-transects (0-500 m) measured 
from potential sources including horizontal and vertical e3diaust vents, 
tailing areas and mills (Fig. 2). 

Cotitction oi l^atthlal 

Only the top living portions (3-4 cm) of lichen and moss clumps 
were collected to reduce the inclusion of debris and possible soil contam- 
ination. Composite samples were placed in paper bags, transported to the 
laboratory, and were dried and stored in these bags until used. 

CldajfUng oi Sample 

The collected lichens and mosses were soaked in distilled water 
and were then thorou^ly washed under running distilled water. Debris and 
discoloured parts of the san^ile were removed. The washed samples were 
allowed to air dry and were subsequently crushed and ground in a mortar 
with a pestle using liquid nitrogen to facilitate the process. The result- 
ant powder was passed through a 70-mesh stainless steel sieve, was oven 
dried at 80* C for 24 h, and was then stored in sealed vials which were 
kept In a desiccator until the analysis. 

ElummtaJi htaty^-U 

Sample preparation . Two approaches were taken in readying the 
aaiiq)les for analysis. For the determination of iron, nickel, lead and 
titanium, 2 g quantities of the powdered materials were pressed into 
pellets of 32 mm diameter. For improved durability and handling, a small 



)WiW«T»'w»i"w.\»y 



345 

amount of wax was mixed in prior to pelleting. Additional details are 
provided In Tomassini et al . , 1976. The second approach was dictated 
by the low levels of uranium present in the lichen and moss samples. In 
this case, 5 g samples of ground material were ashed at 500'C. Subsequently, 
30 mg of the ash were placed between two thin mylar sheets clamped onto a 
plastic sample holder suitable for the spectroscopic measurements. 

Analytical procedure . Samples were analyzed for Fe, Nl, Pb , 
Ti and U by X-ray fluorescence spectrometry (XRP) . In the case of the 
first four elements mentioned, a single standard pellet of known element 
content was used to calibrate the spectrometer after every seven samples. 
Additional detail is provided by Tomassini et al . (1976). A similar 
approach was taken for the uranium analysis. Standard ash samples were 
prepared by adding aliquots of solutions of this element to powdered 
samples of Cladonia rangiferina prior to ashing. The standard material 
had been collected on Manitoulin Island and contained no measurable 
uranium. For an independent check, ten of the analyzed ashed samples 
were subjected to analysis for uranium by neutron activation at the 
University of Toronto Slowpoke Neutron-activation Centre. Excellent 
agreement was obtained over the entire concentration range observed 
in our study (0 - 150 ppm. dry wt) . 

Statistical analysis . The analytical data for a total of 
109 lichen and 98 raoss samples including 36 cryptogamic samples from 
the Agnew Lake uranium mine vicinity, were subjected to statistical 
analyses using modified programs of the University of Pittsburgh Social 
Sciences Statistical Package (Nie et al. . 1975) . All work was executed 
on the Laurentian University DEC 2020 computer. 



346 



3. RESULTS 

ReXativt Accwrtatcutlon Indict 

For a nuni)er of mosses and lichens the ability to accumulate 
Fe, Ni, Pb, Ti and U relative to that observed for Cladonia rangiferina 
Is compared in Table 1. It is evident that Cladonia mitis and 
Cladonia rangiferina had similar metal contents. Pakarinen et al. (1978) 
have indeed predicted low variability for the trace elemental contents 
for members of the genus Cladonia . The Stereocaulon sp. collected 
accumulated up to three times as much as the Cladonia species. Similar 
differences in affinity were also seen for the mosses. Accumulation 
tendencies of the Sphagnum and Polytrichum species in Table 1 were of 
comparable magnitudes, although somewhat weaker than that observed 
for Cladonia rangiferina . In contrast, the Pleurozium and Dicranum 
species both exhibited relative accumulation indices of about 2. 

Differences in accumulation ability of lichens appear to be 
correlated with thallus morphology (smooth versus rough and pitted 
surfaces; and loosely versus tightly packing of the thallus). Similar 
macro-morphological arguments have been presented for mosses (Pakarinen 
and Rinne, 1979) . In addition, microscopic examination of lichen tissue 
have revealed considerable variation in the volume of free space, and 
thus differences in the nun^er and size of interstitial crevices available 
for particulate trapping (Richardson and Nieboer, 1980; Nieboer and 
Richardson, 1980) . 

We may conclude from the data summarized in Table 1 that choice 
of species is an in^ortant principal in environmental assessment work with 
lichens and mosses. It is helpful to know when planning future field 
sampling programs that Cladonia mitis and Cladonia rangiferina samples are 



3A7 

complementary. Similarly. Pleurozium schreberi and the Dicranum 
species are interchangeable, as well as Polytrlchuip connnune and the 
Sphagnum species. 

fJidtat VliVilbution VattoJun^ 

The data plotted in Figures 3 and A reveal an exponential 
dependence of the uranium content with distance for cryptogams. For the 
lichen Cladonia rangiferina a rapid decline in uranium levels coincided 
with the increase in distance between the collection site and the Elliot 
Lake mining and milling operations. Data for Cladonia mitis also 
conformed to the illustrated curve. Furthermore, a curve of similar 
shape was observed for Pleurozium schreberi , although as predicted from 
the relative accumulation indices in Table 1 the uranium levels were 
generally higher at all sites along the transect for this moss. Typical 
uranium versus distance curves over short distances from emission sources 
are shown in Figure 4. For these micro-transects, the fall-off patterns 
with distance of the Fe, Ti and Pb contents resembled those shown for 
uranium. No strong distance dependence was discerned for Ni. 

It is concluded from the above and other data (Richardson et al. , 
1979) that the sphere of influence of vertical exhaust vents extends 
up to 300 m, while the greatest effect along the Elliot Lake macro-transect 
is apparent within the first 10 km. 
?0JvticulaJ:2, TfiapplyiQ 

Unequivocal evidence for the accumulation of inorganic dust in 
lichens and mosses is provided in Figure 5. Since the shapes of the 
curves in Figures A and 5 are similar, it is concluded that uranium 



348 
deposition parallels the fall-out of dust. Similar conclusions may be 
drawn for Fe , Pb and Ti. Consequently, the amount of non-combustible 
inorganic residue present in cryptogams provides a clear indication of 
the severity of dust deposition. 
Ihon-TAXanlim Pottation Tnde,x 

In Fig. 6, the iron content of all Cladonia rangiferlna and 
Cladonia mitls samples are plotted against the corresponding titanium 
levels. The displayed data may be fitted arbitrarily to two linear 
segments with slopes of 6.9 Jig Fe/ug Ti (lower portion) and 15.3 ug Fe/ 
yg Ti (upper segment). As a first approximation » points describing the 
lower segment would fall on the distance-independent portions of curves 
like those exhibited in Figure 7. Thus these data correspond to collection 
sites not influenced seriously by a nearby point source. As might be 
expected, data defining the upper and steeper segment in Figure 6 
may be correlated with collection sites in the immediate vicinity of 
exhaust vents (< 200 m) . Hence these data points correspond to the 
steeply rising portions of the Fe/Ti ratio versus distance curves in 
Figure 7. 

Values of the slopes for Fe versus Ti content plots between 
6,5 and 7.2 have been predicted on the basis of the average composition 
of the earth crust, including data for the Pre-cambrian Canadian Shield. 
Indeed, such Fe/Ti slope values have been found for particulates in 
lichens from "non-polluted" sites in Canadian Arctic and the Province 
of New Brunswick (Nieboer e^ al . , 1978). The observed slope of 6.9 for 
the lower segment in Figure 6 is thus taken to be diagnostic of background 
dust relatively free o£ either enrichment of iron or titanium. Conversely, 



349 

the slope of 15.3 for the upper segment in Figure 6 would appear to 
signal a local enrichment of iron. Indeed, evaluations of the 
Fe/Ti ratio for Elliot Lake tailings and ores based on chemical analysis 
data yield values near 15 (Rasberry and Gorber, 1978; Raicevlc, 1979). 
It should be emphasized that the Fe/Ti slope values are not equivalent 
to the observed Fe/Ti content ratios for individual samples because of 
the non-zero y-intercept values of the linear segments in Fig, 6 (see 
Nieboer et ^. , 1978). Enhancement of Fe/Ti ratios have also been observed 
for lichen samples collected in the vicinity of the Sudbury nickel smelting 
operations, a known source of iron emissions (Nieboer _et al . , 1978). 

An examination of Pearson correlation coefficients for inter- 
elemental comparisons revealed that for all sites examined and for all 
species of lichens and mosses collected, there was a strong linear 
correlation (p < 0.001) between the iron and titanium levels, as well as 
for the uranium and lead contents. Additional strong linear correlations 
were observed for samples collected in the vicinity of direct primary 
sources, such as exhaust vents, for the pairs uranium and iron, and 
titanium and uranium. The correlation between nickel and uranium levels 
was only weakly significant (p < 0.01). The prominence of U, Fe, Ti and 
Pb , and the lesser importance of Ni, are consistent with the known comp- 
osition of the Elliot Lake ores and tailings (J. A. Robertson, 1968; 
S.M. Roscoe. 1969; Murray and Moffett, 1977; Rasberry and Gorber, 1978; 
Raicevic, 1979). This agreement is interpreted as evidence that the 
elemental content of lichens and mosses from the Elliot Lake area 
correctly characterize the environmental impact of the mining and milling 
operations there . 



350 

4. PRESENT AND FUTURE WORK 

The work completed to dace has illustrated the real potential of 
employing lichens and mosses in environmental assessments of impingement 
patterns from the Elliot Lake mining/milling operations. Further sampling 
of Cladonia rangiferina and Pleurozium schreberi was completed this past 
summer. Collections along transects from active dry- and wet-tailing 
sites were emphasized. Appropriate analysis of this newly collected 
material is underway. 

Good progress Is being made in the development of an atomic ab- 
sorption spectrophotometric (AA) method suitable for the routine analysis 
of uranium at sub-microgram level. The approach taken consisted of 
lining the graphite tube of the electrothermal furnace with tantalum foil 
and employing K as a deionizer. Both of these steps have improved the 
sensitivity, and permit routine determinations with a detection limit 
< 40 ng/ml using a 20 pi sample. Additional improvements in sensitivity and 
precision are expected as small technical difficulties in the design and 
manufacture of the tantalum inserts are overcome. The AA method is ideal 

for laboratory uranium uptake and toxicological studies. Preliminary work 

2+ 2+ 

with lichens indicates that UO replaces extracellular Ca , and that the 

neutral liganded forms of the uranyl species are apparently taken up 
intracellularly . Damage to plant tissue is being assessed by measuring 
the degree of K efflux into the uranium incubation medium and by 
monitoring changes in the C photosynthetic fixation rates after the 
metal-uptake step. 

Another promising development has been the identification of 
radioisotopes in cryptogamic samples by alpha spectroscopy. A typical 
alpha spectrum is shown in Fig. 8 and was derived from a sample of the 
moss Polytrichum commune . Many of the daughter isotopes for both 



351 



the Uranium-238 and Thoriuin-232 series are identified. The experimental 
procedure involves fusing the vegetation ash with potassium pyrosulphate, 
removal of the transition metals by electrolysis in 0.3 M sulphuric acid, 
and electroplating of the radioisotopes from mildly acidic solution onto 
stainless steel ct -counting planchets . To date, excellent uranium 
recoveries have been observed for synthetic aqueous standards. Improvements 
in the final electrochemical plating process are required before routine 
quantitation of radioisotope concentrations is possible in cryptogamic 
samples. Additional method development is expected to overcome these 
dificiencies in quantitative recovery work. 

5. CONCLUSIONS 

It has been demonstrated that the element content of lichens and 
mosses clearly reflect local impingement and atmospheric deposition 
patterns. The systematic decrease in non-confcustible inorganic dust and 
in indicator elemental concentrations with distance along macro-transects 
from the Elliot Lake mining and milling operations, and along micro-transects 
from primary sources such as exhaust vents, allows an assessment of the 
effective sphere of influence. We may also conclude from the preliminary 
results described in this paper that the monitoring of the major elements 
Fe, Pb, U and Ti can be a good Indicator of the distribution of radio- 
isotopes. The established fall-out patterns of the major elements will 
no doubt be useful in the planning of detailed radioisotope studies. 



352 



ACKNOWLEDGEMENTS 

Professional assistance from Miss Pat Lavoie, Miss Dilva Padovan 
and Miss Emelie Lamothe is gratefully acknowledged. Appreciation is 
also extended to Mr. C. Chakriavati (Denison Mines) and Mr, A. Vivyunka 
(Rio Algom Mines) for their cooperation in arranging the field 
collections. Assistance in the computer analysis from Dr. Roger Pitblado, 
Department of Geography, Laurentian University is gratefully acknowledged. 
And finally, we wish to thank Professor K. Winterhalder, Department of 
Biology, Laurentian University for helpful discussions, and Dr. David 
Balsillie, Chief, Air Quality Technical Support Section, Ministry of the 
Environment, Sudbury, Ontario, for his able assistance and encouragement 
in his capacity as project liaison officer. 



353 



REFERENCES 

Murray, D. and Mof fett , D. 1977. Vegetating the uranium mine tailings 
at Elliot Lake, Ontario. J. Soil Water Conserv. ^: 171-174. 

Nie, N.K., Hull, C.H. , Jenkins, J.G., Steinbrenner , K. and Bent, D. , 

1975. Statistical package for the social scientist, 2nd ed. McGraw-Hill, < 

New York. 

Nieboer, E. and Richardson, D.H.S. 1980. Lichens as monitors of atmos- ;. 

pheric deposition. In Atmospheric input of pollutants to natural waters, 
edited by S.J. Eisenreich. Ann Arbor Science Publishers Inc., 
Ann Arbor, Michigan. In Press. 

Nieboer, E. , Richardson, D.H.S. and Tomassini, F.D, 1978. Mineral uptake 
and release by lichens; an overview. Bryologist 81: 226-246. 

Pakarinen, P. and Rinne, R.J.K. 1979. Growth rates and heavy metal concent- 
rations of five moss species in paludified spruce forests. Lindbergia 5: 
77-83. 

Pakarinen, P., Makinen, A and Rinne, R.J.K. 1978. Heavy metals in Cladonia 
arbuscula and Cladonia mitis in eastern Fennoscandia. Ann. Bot . Fennici 
15: 281-286. 

Raicevic, D. 1979. Decontamination of Elliot Lake uranium tailings. CIM 
Bulletin (August issue) : 1-7. 

Rao, D.N., Robitaille, G. and Leblanc, F. 1977. Influence of heavy metal 
pollution on lichens and bryophytes. J. Hattori Bot. Lab. 42: 213 -239. 

Rasberry, J.M. and Gorber, D.M. eds . 1978. Environmental assessment of the 
proposed Elliot Lake uranium mines expansion. Report by J.F. MacLaren 
Ltd., in 4 volumes. 

Richardson, D.H.S. and Nieboer, E. 1980. Surface binding and accumulation 
of metals in lichens. In Cellular interactions in symbiosis and parasitism, 
edited by C.B. Cook, P.W. Pappas and E.D. Rudolph. Ohio S^ate University 
Press, Columbus, Ohio, pp. 75-94. 

Richardson, D.H.S., Beckett, P.J. and Nieboer, E. 1980. Nickel in lichens, 
bryophytes, fungi and algae. In Nickel in the environment, edited by 
J.O. Nriagu. John Wiley and Sons, Inc., New York, pp. 367-406. 

Richardson, D.H.S., Nieboer, E., Beckett, P.J., Boileau, L., Lavoie, P. 
and Padovan, D. 1979. The levels of uranium and other elements in lichens 
and mosses growing in the Elliot Lake and Agnew Lake areas, Ontario, 
Canada. Report to the Ontario Ministry of the Environment. 71 pp. 

Robertson, J. A. 1968. Geology of Townships 149 and 150. Geological Report 
57, Ontario Department of Mines (Ministry of Natural Resources), Toronto, 
Ontario, pp. 76-125. 



354 



Roscoe, S.M. 1969. Huronian rocks and uraniferous conglomerates. Geological 
Survey of Canada Report 68-AO . Department of Energy, Mines and Resources, 
Ottawa, Ontario. 

Svoboda, J. and Taylor, H.W. 1979. Persistence of cesium-137 in arctic 
lichens, Dryas integrifolia , and lake sediments. Arct. Alp. Res. 11: 95-108. 

14 
Tomassini, F.D. 1976. The measurement of photosynthetic C fixation rates 

and potassium efflux to assess the sensitivity of lichens to sulphur dioxide, 

and the adaptation of X-ray fluorescence to determine the elemental content 

in lichens. M.Sc. Thesis, Laurentian University, Sudbury, Ontario. 

Tomassini, F.D., Puckett, K.J.. Nieboer, E., Richardson, D.H.S. and Grace, B. 
1976. Determination of copper, iron, nickel and sulphur by X-ray fluorescence 
in lichens from the Mackenzie Valley, Northwest Territories, and the Sudbury 
District, Ontario. Can. J. Bot. 54: 1591-1603. 



TABLE 1 Comparative Trace-element Levels in Lichens (L) and Mosses (M) 

Ratios are computed for each species against the corresponding elemental 
content of Cladonla rangiferina . Only those sites where species occur in 
common with Cladonia rangiferina are used in calculation of the ratios. 
Ratios are expressed as mean ± 1 standard error; values greater than 1.00 
denote enhancement . 

Species Elemental ratio Number of sites 

where both species 
Iron Nickel Lead Titanium Uranium occur in common 

Cladonia mitls (L) 1.07 ± 0.05 0.95 ± 0.03 0.90 ± 0.05 1.10 ± 0.05 0.97 ± 0.11 $§ 

Stereocaulon sp. (L)^ 2.66 ± 0.32 1.92 ± 0.27 1.27 ± 0.06 3.43 ± 0.38 2.22 ± 0.21 6 

Pic ran urn spp . (M)^ 2.51 ± 0.81 2.73 ± 0.60 2.33 ± 0.72 1.95 ± 0,56 1.48 ± 0.09 4 

Pleurozium sclireberi (M) 1.69 ± 0.11 1.84 ± 0.15 1.94 ± 0.19 1.38 ± 0.09 1.91 ± 0.18 t% 

Polytrichum commune (M) 0.77 ± 0.15 1.09 ± 0.15 0.95 ± 0.16 0.80 ± 0.24 1.02 ± 0.19 10 

Sphagnum spp. (M) "^ 0.87 ± 0.24 1.07 ± 0.13 1.02 ± 0.13 0.76 ± 0.19 1.07 ± 0.51 10 

a Likely Stereocaulon paschale but taxonomically a difficult group in which to 

differentiate species; L denotes lichen. 

% Two species: Dlcran i yi vlride and Dicranum montanum , often mixed together; 

M denotes moss . 

e Five species; mostly of the Sphagnum acutifolium group 






356 



LEGENDS TO FIGURES 

Fig. 1. Area map indicating collection sites for the Elliot Lake 
macro-transect . 

Fig. 2. Area map showing micro- transect collection sites in the 
vicinity of the Rio Algom and Denison Mining and 
Milling operations. Collections were made at four other 
sites located south of the area shown. Two sites were 
adjacent to Horn Lake, and the other pair were close to the 
Nordic *01d' tailings area. 
The symbols are defined as follows: 

, Road or highway; \J , Water; — — , Tailing; 

I , Horizontal mining exhaust vent;l— 1, Vertical 
mining exhaust vent; ''**, Micro-transect collection site; 
^1 , Building. 

Fig, 3. Lichen uranium content of Cladonla rangiferina as a function of 
distance along the Elliot Lake macro-transect. 

Fig. 4. Uranium content of some lichens and mosses as a function 
of distance from the vertical exhaust on Knowles Island 
(site 1, Fig. 2). 

Fig. 5. Percentage content of non-combustible, inorganic ash in 

cryptogams as a function of distance of the collection site 
from the Quirke-IE Mine horizontal exhaust vent (site 
4. Fig. 2). 

Fig. 6. The relationship between the iron and titanium contents of 
Cladonla rangiferina and Cladonla mitis . Data from all 
macro- and micro-transects are represented. The slopes of 



357 



Fig. 6. continued 

the arbitrarily placed segments evaluated by linear 
regression were 6,9 (lower segment) and 15.3 (upper segment). 

Fig. 7. Variation of the iron/titanium ratio for lichen and moss 
samples with distance of Che collection site from the 
Quirke-IE Mine horizontal exhaust vent (site 4, Fig. 2). 

Fig. 8. Alpha spectrum for a sample of Polytrichum commune collected 
near a mill. The various radioisotopes present 
correspond to the Uranium-238 and Thorium-232 decay schemes. 
The 1024 channel analyzer was adjusted to a resolution of 
11.0 keV per channel and was calibrated with an Americium-241 
standard source. 



MACRO-TRANSECT 



358 




? ? 'o to n \^fY\ 



• COLLECTION SUE 

• MINING OPERATION 
+ EJ VILLAGE AND TOWN 

* HIGHWAY 



LAKE HURON 



T^>^^l ChluW ^ A.) 



^IL- 



359 




T'.<^UTC % (.>i\AotV ft-t ^.) 



360 



E 



12-1 



9.7 



hO 



Cladonia rangiferina 




10-8 21.6 32.^ 43.2 5/»:0 

DISTANCE FROM ELLIOT LAKE (km) 



Vc^o^rc 1 C ^iuW^ at £^. ) 



361 



40 



30 



LU 



^ 20 

o 
u 



10 




• Cladonla sf^ 
■ Dlcrinum spp. 



DISTANCE 



100 

FROM VERTICAL 



200 300 

EXHAUST VENT KNOWLES ISLAND 



400 



h) 



Tcwre M Cl^feUcv- ^ «J.) 



362 




100 200 300 400 

DISTANCE FROM VENT,m 



Tcj^ure. S" C^t^^eW^ jejt «-^ . ) 



363 




50 100 150 200 

TITANIUM CONTENT, ppm 



R^riL L CriieVxrtr ct *J.) 



364 




MOSSES 

X,Polytrichum commune 
P, Pleurozium schreberi 
S, Sphagnum spp. 

LICHENS 

0, Clodonia spp. 
V, Umbilicaria spp. 



p^ 

^-0-^-0- -8- -0^--^ 



100 200 300 

Distance, m 



400 



500 



Tc^uro.-] (,bl\eWr ^ ^ • J 



365 




210 



POLYTRICHUM MOSS 
, 2705 MIN. 



,„ 2(8 212 2f6 

h PoBi ,Po 



yg^Bi . iV. 



i 



• 


212 


214 


Po 


.Po 


I 


A , 


,/\. 



320 400 



480 560 640 

CHANNEL NO. 



720 



800 



X-Cc^rt % C r4uUr ct ^.) 



T 



366 



ACID RAIN - AN OVERV IE W 



TECHNOLOGY TRANSFER CONFERENCE 



NOVEMBER 25. 1980 



E. W. PICHE 



367 



ABSTRACT 



This paper will outline the evolution of the Ontario 
Government's recognition, concern, ultimate actions, 
and overall strategy with relation to the acidification 
of precipitation phenomenon. specifically, key turning 
points from both the scientific and the evolutionary 

VIEWPOINTS WILL BE MENTIONED. In ADDITION, ONTARIO'S 
TECHNICALLY COMPREHENSIVE PROGRAM WILL BE REVIEWED. 



368 



Introduction 

Atmospheric water in equilibrium with carbon dioxide 
theoretically will have a ph of 5.6. experimental 
observations made as part of the sudbury environmental 

AND LaKESHORE CAPACITY STUDIES OVER A PERIOD GREATER 

than five years^ led scientists working for the ontario 
Ministry of the Environment to the conclusion that the 
acidity of rain falling in large areas of ontario was 
far greater than that predicted by the aforementioned 

EQUILIBRIUM. In FACT> IN AN AREA RANGING ROUGHLY FROM 

Sudbury east to Kingston and south to Toronto^ the 

AVERAGE pH OF PRECIPITATION RANGES FROM 4.0 - 4.5. 

The pH scale is a logarithmic scale used to reference 

AND compare free HYDROGEN ION CONCENTRATIONS IN SOLUTION. 

The SCALE runs from roughly 1.0 to 14.0 with 7.0 being 

NEUTRAL, NUMBERS LESS THAN 7,0 INDICATING ACIDS AND 
THOSE GREATER THAN 7.0 INDICATING BASES. An IMPORTANT 
FEATURE OF THIS SCALE IS THE FACT THAT A PH CHANGE 
FROM 7.0 TO 5.0 CORRESPONDS TO AN INCREASE IN ACIDITY 
OF 10 TIMES. A CHANGE OF PH FROM 7.0 TO 5.0 REPRESENTS 
A HUNDRED-FOLD INCREASE IN THE ACIDITY CONCENTRATIONS 

AND SO ON. Table One lists the pH of some common 

MATERIALS. 



369 



table one 
ph of common materials 



MATERIAL pH 



VINEGAR 2.2 

APPLES 3.0 

SAUERKRAUT 3.5 

TOMATOES i».2 

CARROTS 5.0 

SALIVA 5,7-7.1 

MILK 5.6 

HUMAN URINE 7.4 

SEA WATER 8.3 

0.1 M NHz 11.2 



Source ; W, L. Masterton and E, J. Slowinski, 

Chemical Principles (Philadelphia^ Pa.: W. B. Saunders Co., 

1959), p. 428. 



370 



Currently, it is felt that the reason for this unnatural 

ACIDITY concentration IN PRECIPITATION IS THE FACT 
THAT^ CONCOMITANT WITH INCREASES IN INDUSTRIAL ACTIVITY 

BY Man over Continental North America in the past 25 

YEARS, THERE HAVE BEEN SIGNIFICANT INCREASES IN EMISSIONS 

OF OXIDES OF NITROGEN AND SULPHUR. ThE PRINCIPAL CONTRIBUTORS 

ARE FROM THE GENERATION OF ELECTRICITY BY THERMAL 

MEANS USING COAL AND OIL AS FUELS AND THE NON-FERROUS 

SMELTING INDUSTRY. 

Of GREATER IMPORTANCE AND RELEVANCE TO THIS PHENOMENON, 
IS THE FACT THAT OVER THE PAST 15 YEARS, AS A CONSEQUENCE 
OF THE 1960'S DICTUM OF "ThE SOLUTION TO POLLUTION Is 

Dilution", a large number of very tall, of the order of 

500 FT. or more, SMOKESTACKS HAVE BEEN ERECTED OVER 

EASTERN Continental North America in an attempt to 

MEET ground LEVEL CONCENTRATION CRITERIA SET BY WELL- 
MEANING local REGULATING AGENCIES. 

Further, the installation of electrostatic particulate 

REMOVAL devices HAS SEEMINGLY FURTHER EXACERBATED THE 
problem by REMOVING FROM THE EMITTANTS, SOME INHERENT 

neutralization capacity. 

Together, these events have contributed to the current 
problem of the very high level of acidic loadings to 
Ontario's environment. 






371 



FVQLUTIQN OF QNTARIO^S INVQLVEtCNT 

As NOTED EARLIER, RECOGNITION OF THE PROBLEM CAME AS A 
CONSEQUENCE OF PRECIPITATION MEASUREMENTS ASSOCIATED 

WITH THE Sudbury Environmental and Lakeshore Capacity 
Studies. Additional key events leading to the instigation 

OF A major environmental PROGRAM BY THE ONTARIO MINISTRY 

OF THE Environment are as follows: 

On June 21^ 1977 the Honourable R, LaBlanc referenced 
the long-range transport of air pollutants problem in 
A formal address given at the Air Pollution Control 
Association Conference which was held in Toronto. 

On October 2h 1977 the Ontario Ministry of the Environment 
released a report entitled "Acidic Precipitation In 
South-Central Ontario: Recent Observations." This 
report received wide-spread publicity. 

On March 27, 1978, the Ontario Ministry of the Environment 
released its Sudbury Environmental Study report entitled 
"Extensive Monitoring of Lakes in the Greater Sudbury 
Area, 1974-1975" by Conroy et.al. This report essentially 

OUTLINES the RESULTS OF A THREE-YEAR SAMPLING PROGRAM 
on SOME 200 LAKES WITHIN A 200 KM RADIUS OF SUDBURY. 



372 



The outstanding feature of this document was that it 

INDICATED THAT ROUGHLY 20X OF THOSE LAKES WERE IN A 

rather deteriorated state with respect to their water 
column free hydrogen ion concentration and an additional 
50% were categorized as being very vulnerable. 

On June 7. 1978, a key turning point in the instigation 

OF investigations with RESPECT TO THIS PHENOMENON OCCURRED 
AS A CONSEQUENCE OF AN ARTICLE IN THE TORONTO StAR 
ENTITLED "RAIN OF POLLUTION KILLING RESORT LaKES." 

This article was based on data presented in a paper 

GIVEN AT THE GrEAT LaKES MEETING BY Mr. W. SCHEIDER. 

AN Ontario Ministry of the Environment employee, in 
May. 1978. 

In July of 1978, the Ontario Ministry of the Environment 
revoked the INCO Control Order giving INCO a four-year 
reprieve. This was followed by the instigation of the 
Acidic Precipitation In Ontario Study in October 1978. 

In November of 1978, the Bilateral Research Consultation 
Group was formed as a part of the Federal Government's 
recognition of the long-range transport of air pollutants 
phenomenon. 

In February of 1979, a presentation was made to the 



373 



Legislature of the Province of Ontario Standing Committee 

ON Resources Development. This was a presentation on 

acidic precipitation and abatement of emissions from 

INCO operations at Sudbury, The recommendations of this committee 

WERE published IN JUNE 1979 AND LATER REVISED IN FINAL 
FORM AND PUBLISHED IN OCTOBER 1979. 

On July 26^ 1979^ Canada and the U.S. signed a joint 

STATEMENT AGREEING TO DEVELOP A COOPERATIVE BILATERAL 
AGREEMENT ON AIR QUALITY. ThIS WAS FOLLOWED IN OCTOBER 
1979 BY THE RELEASE OF THE FIRST CaNADA/U.S. BiLATERAL 

Research report entitled "The LRTAP Problem in North 
America: A Preliminary Overview." 

On October 25> 1979 a statement on acidic precipitation 
TO the Legislative Estimates Committee was made by the 
Honourable Harry Parrott. 

On November 1. 2, and I, 1979^ an internationally 
recognized seminar on acidic precipitation was held in 
Toronto. This seminar^ more than any other single 
event^ highlighted the international significance^ 
interest^ and recognition given this problem. Over 
700 attendees from many countries as well as Canada 
and the U.S. participated actively. 



374 



On January 18, 1980, the Honourable Harry Parrott met 
WITH Mr. D. Costle and the Honourable John Fraser to 

DISCUSS A WORKING AGREEMENT ON ACID RAIN. ThIS ACTIVITY 

finally culminated in the signing of a memorandum of 
Intent with the establishment, on August 5, 1980, of 

FIVE working GROUPS WITH VERY STRINGENT DEADLINES. 

Ontario has representation on all five groups, in 
recognition of its technical expertise and historically 
active role. 



375 



Fl FMFNTS OF APPROACH 

The problem then^ is the increased free hydrogen ion 
concentration in precipitation which is believed to be 
associated with emissions of oxides of sulphur and 
nitrogen. 

In ORDER TO DEAL WITH THIS PROBLEM, THE ONTARIO MINISTRY 

OF THE Environment established three committees. They 

ARE THE STEERINGv SCIENTIFIC AND ECONOMIC STUDIES 

Committees. The Steering Committee is responsible for 

overall study, strategy and policy recommendations. 

The Scientific and Economic Studies Management Committees 

ARE responsible FOR DESIGNING AND IMPLEMENTING SPECIFIC 

studies. The objective is to "Protect The Environment." 

The process of problem definition to government policy 
is represented diagrammatically in Figure One, 

In order to simplify the approach to this very complex 
phenomenon, the steering committee established five 

MAJOR DIVISIONS OF STUDY. ThEY ARE: 

( i) Sources 
( ii) Meteorology 
(ill) Deposition 



376 



PROBLEM DEFINITION 



INFORMATION REQUIREMENTS 



SCIENTIF 




C STUDIES 



ECONOMIC STUD 




INFORMATION 
ASSIMILATION 
AND SYNTHESIS 



POLICY 
RECOMMENDATION 



GOVERNMENT POLICY 



FIGURE ONE 



377 



( iv) Effects 

Primary - Aquatic and Terrestrial 
Secondary - Aesthetics^ such as visibility 
impediment^ materials and human 
Health 

( v) Socio-EcoNOMic Aspects 



378 



S OURCES 

Figure Two presents Eastern North American SO2 emitting 

GEOGRAPHICAL AREAS. ThESE GEOGRAPHICAL AREAS ARE 
DEFINED ON GRIDS OF 150 X 160 KM. ThE U.S. EMISSION 

rates are from the sure ii data base 1977-1978 emission 
rates for point sources^ and 1973-1977 emission rates 
for area sources. canadian data are from environment 
Canada and are estimated 1977 emission rates for major 
SO2 point sources and 1974 emission rates for other 

POINT sources and AREA SOURCES. 

Thirteen geographical areas are listed in order that 
the noranday quebec operations could be included. 
Table Two lists the geographical areas with their 

RESPECTIVE EMISSION QUANTITIES. ThE MOST IMPORTANT 
sources of oxides OF SULPHUR ARE THE NON-FERROUS SMELTING 
INDUSTRIES, 2.2 X 10" TONNES/YR., AND OTHER INDUSTRIAL 
PROCESSES, 1.1 X 10^ TONNES/yR. (AlTSHULLER AND 

McBean, 1979 - See Bibliography) 

In Figure Three, similar emissions are listed for 
OXIDES OF nitrogen, The Toronto area ranks as #9, 
The primary sources of NO^ in Eastern Canada are from 

AUTOMBILES - 1.2 X 10^ TONNES/YR. WITH UTILITY COMBUSTION 
making up APPROXIMATELY 0,2 X 10° TONNES/yR. (AlTSHULLER 

AND McBean, 1979). 



379 



Table Three similarily lists the major NO^ geographical 

AREAS. 



380 



MAJOR SOj EMITTING^GEOGRAPHICAL AREAS 




ATLANTiC 
OCEAN 



N-'' 



FIGURE TWO 



381 



EASTERN NORTH AMERICA - MAJOR SO^ EMITTING GEOGRAPHICAL 

AREAS* 



GEOGRAPHICAL AREA 



GRAMS/SECOND 



** 



1. East and West Pittsburg; Ohio 
River Valley; W. Virginia 

2 . Sudbury , Ontario 

3. W. Kentucky; Louisville; 
S. Indiana 

4 . Toledo , Ohio; Detroit , 
Michigan 

5. Lower and Central Ohio 
River Valley; W. Virginia 
(Clarksburg) 

6. East and West Cincinnati; 
Northern Kentucky 

7. New York; New Jersey 

8. West Illinois; East 
Missouri 

9 . Indianapolis, Indiana 

10. Mobile, S. Alabama 

11. Chicago, Illinois 

12. Western Kentucky 

13. Rouyn-Noranda, Quebec 



75,586.0 

43, 617.8 
41,462,5 

40,117.7 

33,863.8 

33,514.4 

29,868.1 
29,514.9 

23,507.3 
23,352.5 

22,173.7 
21,281.2 
16,336.0 



* Geographical Area is defined as 160 km x 160 km 
grid square. 

** The U.S. emission rates are from the SURE II data 

base and are 1977-78 emission rates for point sources, 
and 1973-77 emission rates for area sources. Canadian 
data are from Environment Canada and are estimated 
1978 emission rates for major SO^ point sources, and 
1974 emission rates for other point sources and area 
sources. 

30,000 gm/sec. - IMM Tons/yr. 



TABLE TWO 



382 



MAJOR NO EMITTING GEOGRAPHICAL AREAS 




ATLANTIC 
OC£A^ 



\./' 



FIGURE THREE 



383 



EASTERN NORTH AMERICA - MAJOR NO^ EMITTING GEOGRAPHICAL 

AREAS* 



GEOGRAPHICAL AREA GRAMS /SECOND ** 

1. New York; New Jersey 52,024,1 

2. Chicago, Illinois 30,867.0 

3. Toledo, Ohio; Detroit, 25,303.9 
Michigan 

4. East and West Pittsburg; 23,132.7 
Upper and Central Ohio 

River Valley 

5. Cincinnati, Ohio; Northern 16,536.6 
Kentucky 

6. Cleveland, Ohio; West 15,541.0 
Pennsylvania 

7. West Kentucky; South 12,161,2 
Indiana 

8. East Missouri; West 11,783.9 
Illinois 

9. Toronto, Ontario 11,078.1 
10. South Louisiana 10,117.8 



* Geographical Area is defined as 160 km x 160 km grid 
square. 

** The U.S. emission rates are from the SURE II data base 
and are 1977-78 emission rates for point sources, and 
1973-77 emission rates for area sources. Canadian data 
are from Environment Canada and are estimated 1978 
emission rates for major SO point sources, and 1974 
emission rates for other point sources and area 
sources. 

30,000 gm/sec. = IMM Tons/yr. 



TABLE THREE 



384 



The relationship between emissions of oxides of sulphur 
and nitrogen and the resultant precipitation acidity is 
NOT KNOWN. However, it is reasonable to conclude that 

THERE is a 1:1 relationship BETWEEN TOTAL EMISSION 
QUANTITY AND THE ULTIMATE ACIDITY OF PRECIPITATION, AT 
LEAST TO A FIRST APPROXIMATION. CONSEQUENTLY, FiGURE 

Four combines emissions of SO2 and NO^. In this manner, 
THE Canadian emissions rank 8th, 14th and 15th respectively, 
thereby pointedly demonstrating the significance of 
continental sources as they relate to this problem. 

Finally, Table Four combines and ranks the data from 
Tables Two and Three (presented in Figure Four). 

The significance of the distribution of significant 
sources will become more obvious when the meteorological 
aspects of this problem are outlined, 

Turning now to Ontario, Table Five lists the ten major 

EMISSION sources FROM THE ONTARIO INVENTORY INFORMATION 

system FOR 1978. The emissions for INCO are reduced 
substantially over normal emissions as 1978 was a 
strike year. In addition, note that the bracketed 
level of 1.137 n tonnes is in fact the current emission 
level allowed under the new Regulation issued to INCO 
on August 28, 1980, 



MAJOR SOg AND NO^ EMITTING GEOGRAPHICAL AREAS 




FIGURE FOUR 



386 



EASTERN NORTH AMERICA - MAJOR SO AND NO EMITTING 

GEOGRAPHICAL AREAS* 



GEOGRAPHICAL AREA 



GRAMS/SECOND** 



1. East and West Pittsburg; 
Upper and Central Ohio 
River Valley 

2. New York; New Jersey 

3 . Toledo , Ohio; Detroit 
Michigan 

4. Western Kentucky; South 
Indiana 

5. Chicago, Illinois 

6 . Cincinnati , Ohio; North 
Kentucky 

7 . Cleveland , Ohio; West 
Pennsylvania 

8. Sudbury, Ontario 

9. Lower and Central Ohio 
River Valley; Clarksburg, 
Virginia 

10. East Missouri; West Illinois 

11. Indianapolis , Indiana 

12. Western Kentucky 

13. Mobile; South Alabama 

14. Toronto, Ontario 

15. Rouyn - Noranda, Quebec 

16 . Southern Louisiana 



98,718.7 

81,892.2 
65,421.6 

53,623.7 

53,040.7 
50,051.0 

47,997.7 

43,915.3 
42,401. 3 

41,298.8 
30,202.9 
25,849.3 
24,138.5 
18,584.7 
16,402.2 
14,596.8 



* Geographical Area is defined as 160 km x 160 km grid 
square. 

** Tho U.S. emission rates arc from tiic SURE It data 

base and arc 1977-78 emission rates for point sources, 
and 1973-77 emission rates for area sources. Canadian 
data are from Environment Canada and are estimated 
1978 emission rates for major SO^ point sources, and 
1974 emission rates for other point sources. 

30,000 gm/sec. - IMM Tons/yr. 



TABLE FOUR 



ONTARIO SO2 EMISSION 1978 
10 MAJOR EMISSION SOURCES 
IN THE ONTARIO INVENTORY INFORMATION SYSTEM 



SO2 EMISSION 



Emission Source 

1. INCO* 

2. .iANTICOKEv G.S. 

3. Algoma STEELy Ore Division 

4. Lambton^ G.S. 

5. Falconbridge Smelter** 
5. Lakeview^ G.S. 

7. Imperial Oil Ltd. 

8. Lennox, G.S. 

9. Stelco Ltd. 

10. Algoma Steel Corp. Ltd. 



Location 


10-' Tonnes/yr. 


Sudbury 


556.99 


(1.137.0) 


Nanticoke 


183 . 84 




Wawa 


163,29 




Sarnia 


130,89 




Sudbury 


117.03 


( 200.0) 


Toronto 


89.25 




Sarnia 


28.85 




Bath 


21.30 




Hamilton 


16.91 




Sault Ste. Marie 


14,41 






1332.75 


(1.985.74) 



■N-* 



Strike Year; INCO 1977 Annual SO2 Emission 2506.6 x 10^ lb/yr 

- 1.137 Tonnes x 10^/yr. 

Production Cut Back; Falconbridge Smelter 1977 SO2 Emission 
440.9 X 10^ lb/yr. 

- 200 X 10^ Tonnes/yr. 



TABLE FIVE 



388 



The emissions from INCO operations in Sudbury constitute 

THE MOST significant SINGLE-POINT SOURCE OF SO2 EMISSIONS ON 
THE CONTINENT. HoWEVERy IN ONTARIO^ THE SECOND-MOST SIG- 
NIFICANT SOURCE OF SO2 IN A COLLECTIVE MANNER AND A SIG- 
NIFICANT SOURCE OF NO^, ARE THE OPERATIONS OF ONTARIO HyDRO. 

Table Six lists Ontario Hydro's SO2 and NO emissions for 
1979. 

DEPOSITION 

The transfer of acidic materials from the atmosphere to the 
environment is called deposition. The major divisions are 
dry gaseous^ dry particulate^ and all forms of precipitation. 



389 



ONTARIO HYDRO SO2 AND NO^ EMISSIONS FOR 1979 



STATION SO2 (Mg/Year) NO^ •(Hg/Year) 



Windsor 


31 


Thunder Bay 


10.033 


R L Herne 


10,191 


Lakeview 


9L3't7 


J\MBTON 


160.249 


Nanticoke 


155.078 


.ennox 


10.012 


TOTALS 


436.941 




(480.000) 



10 

1.059 

4.291 

13.785 

12.864 

28.650 

992 

61.551 
(58.000)** 



• NOj^ expressed as NO 
** tons/year 



1980; Predicted Levels will be down slightly 



TABLE SIX 



3fi|& 



EFFECTS 

The primary effects of greatest concern are to the aquatic 
biosphere as it is the most susceptible to adverse effects 
from acidic loadings. sport fisheries^ such as the brook 
and lake trout, are the most sensitive to acidification of 

THEIR HABITATS. ThESE FISHERIES ARE AFFECTED BY BOTH THE 
GRADUAL ACIDIFICATION OF THEIR ENVIRONMENT AND THE SO-CALLED 
"spring shock" LOADING, THAT IS, THE SUDDEN RELEASE OF FREE 

hydrogen ions during spring runoff. 

Lake and watershed susceptibility to acidification is directly 

RELATED TO THE LACK OF BUFFERING MATERIALS LIKE CaCOj IN 

A lake's drainage basin. This lack of buffering capacity is 

PROMINENT IN MANY RECREATIONALLY IMPORTANT AREAS OF ONTARIO. 

terrestrial effects, which include soils AND VEGETATION, ARE 
CONTROVERSIAL AT THIS TIME. ThERE IS EVIDENCE TO SHOW 
BENEFICIAL, AS WELL AS DETRIMENTAL, CONSEQUENCES OF INCREASED 
ACIDIC LOADINGS. ThE ULTIMATE RESOLUTION TO THIS QUESTION 

will require many additional years of research. 

Secondary effects such as visibility impediment and material 
damages are other areas of concern and controversey . 
Again, additional investigative research will have to be 



391 



undertaken before the final verdict will be clear to all. 
Finally^ Health effects^ which are related to sulphate 

INHALATION^ ARE ALSO VERY CONTROVERSIAL. DaTA ARE VERY 
SPARSE AND IRRESOLVABLE^ FROM THE CURRENT VANTAGE POINT^ BUT 
CERTAINLY DESERVING OF ADDITIONAL ATTENTION, 

snCIQ-ECQNQMIC ASPECTS 

In order TO DEVELOP A RATIONAL APPROACH TO THE SOLUTION OF 
THE PROBLEM^ IT IS NECESSARY TO BE ABLE TO QUANTIFY THE 
COSTS OF POLLUTION CONTROL AS WELL AS THE ENVIRONMENTAL 
BENEFITS WHICH WILL RESULT, As WITH THE OTHER DIVISIONS^ 
THERE ARE MANY UNANSWERABLE QUESTIONS AT THIS TIME. HoWEVERy 
THE ANSWERS TO QUESTIONS OF ECONOMIC IMPACT WILL BE INSTRU- 
MENTAL IN CATALIZING SOCIETY INTO HAVING THE WILL TO DEAL 
WITH THIS COMPLEX PHENOMENON. 



392 



QNTARIO^S PROGRAM 

■I 
The Acidic Precipitation In Ontario Study's budget for 

Fiscal 1980/1981 is approximately five million dollars. The 

Ontario Ministry of the Environment has four million of 

these funds and The Ontario Ministry of Natural Resources 

has one million. The following constitutes a summary of the 

areas of concentrated activity at this particular time, The 

main divisions are identical to those discussed in the 

previous section. 

Sources 

The intent of this activity is two-fold;,, 

1) To design a system to provide emission data handling to 
assist in the preparation for emission quantities for input 
into the long-range transport models. 

2) To develop and implement a computerized information 
system which will handle the data collected under 1). 

The vast number of individual sources on a continental 
scale, coupled with the fact that there are a myriad of 
means of quantifying emission sources, plus the numerous 
agencies, provincial, state, and federal, makes the collection 

OF A standardized INVENTORY OF EMITTANTS A DIFFICULT TASK. 

Efforts are currently underway to standardize associated 
methodologies. 



:5^^^ 



iJFTRQRQLQGY 

Meteorology includes atmospheric modelling and the collection 

AND compilation OF A VAST QUANTITY OF WEATHER STATISTICS. 

Under the modelling aspect of this activity^ work will be 
continued on the validation of currently developed statistical 
models and investigation of the appropriateness and applicability 

OF OTHER KINDS OF MODELS SUCH AS ThE LaGRANGIAN MoDEL. ThE 
ULTIMATE AIM OF THIS ACTIVITY IS TO MODEL SOURCE-RECEPTOR 
LINKAGES SUCH THAT THE RESULTS OF ABATEMENT ACTIVITIES CAN 
BE PREDICTED BEFORE THE EXPENSE OF ACTUAL ABATEMENT BEGINS. 
The IMPORTANCE OF MODELLING HAS BEEN HIGHLIGHTED BY THE 

RECENT Memorandum of Intent signed by the governments of 
Canada and the U.S. Ontario has representation on this 
group and to date, has maintained a very high profile^ due 
TO the internationally recognized expertise of its scientists. 
Agreement by U.S. and Canadian authorities as to the appro- 
priateness of a specific model or models, will be the most 
signficant forerunner to a treaty between the two countries 
which is imperative if this problem is to be successfully 
resolved. 



394 



DEPOSITION 

As INDICATED EARLIER, MATERIAL IS TRANSFERRED FROM THE 

atmosphere to the environment via several mechanisms. 
These mechanisms include dry gaseous, dry particulate 

AND precipitation IN ALL FORMS. In ORDER TO MEASURE, 
quantify and ULTIMATELY IDENTIFY SPECIFIC SOURCES OF 

these materials, ontario has set up two independent 
networks. 

The Cumula tive Network : At present, Ontario has operating 
throughout the province some 33 monthly cumulative wet 

AND DRY MONITORS. ThE MAJOR FUNCTION OF THESE MONITORS 
IS TO MEASURE, ON A PROVINCIAL BASIS, THE ENVIRONMENTAL 
LOADING OF ACIDIFYING MATERIALS. ThIS WILL ALLOW US TO 

quantify and draw up loading isopleths for all areas of 
the province. 

Event Network : This network consists of monitors from 
which samples will be collected on a daily, that is, 

A 24-HOUR BASIS. It IS CURRENTLY PLANNED THAT THERE 
WILL BE THREE SUCH STATIONS CONSISTING OF FIVE MONITORS 
LOCATED WITHIN A 50 KM RADIUS. ThE CURRENT PROPOSED 
LOCATIONS ARE: KINGSTON^ DORSET. AND LONDON. ThE 
MAJOR FUNCTION OF THIS NETWORK WILL BE TO RELATE, USING 
METEOROLOGY AND THE MODELLING ACTIVITY, THE SIGNIFICANCE 
OF SPECIFIC SOURCES AS THEY IMPACT UPON SPECIFIC RECEPTORS, 
FIRST ON A CONTINENTAL BASIS AND THEN ULTIMATELY ON A 
PROVINCIAL LEVEL. 



%m 



EFFECTS 

As PREVIOUSLY STATEDy THE MOST OBVIOUS AND WIDELY 
DISCUSSED AREA OF DETRIMENTAL EFFECT IS TO THE AQUATIC 

BIOSPHERE. This is a consequence of the fact that a 

GREAT DEAL OF THE EASTERN NORTHERN AMERICAN CONTINENTAL 
ENVIRONMENT IS DEFICIENT IN BUFFERING MATERIALS. MaNY 
STREAMS, RIVERS AND LAKES (TOTAL WATERSHEDS) ARE THEREFORE^ 
QUITE SUSCEPTIBLE TO ACIDIC LOADINGS. 

At THIS PARTICULAR TIME, ONTARIO HAS BEEN DEALING WITH 
THIS PROBLEM ON A PROVINCIAL SCALE. ACTIVITIES TO 
SAMPLE AS MANY LAKES AS POSSIBLE IN THE PROVINCE ARE 
WELL UNDERWAY. SENSITIVE LAKES ARE BEING IDENTIFIED 
AND CLASSIFIED AND SOME OF THEM ARE BEING INCORPORATED 
INTO INTENSIVE CALIBRATED WATERSHED STUDIES. ThESE 
INTENSIVE STUDIES INCLUDE ALL ASPECTS, FROM THE MEASUREMENT 
OF SPECIFIC LOADINGS, THE QUANTIFICATION OF EFFECTS ON 
THE TERRESTRIAL BIOSPHERE, AND ULTIMATELY, TO THE ACIDIC 
INPUT TO LAKES. In PARTICULAR, DETAILED MEASUREMENT AND 
BUDGETING OF MATERIAL INPUTS TO AND FROM THE LAKE AND THE 
ULTIMATE CREATION OF RECEPTOR-EFFECTS MODELS, IS THE OBJECTIVE. 

These models, together with the atmospheric meteorological 

MODELS, WILL ULTIMATELY ALLOW THE QUANTIFICATION OF THE 
SIGNIFICANCE OF CHANGES IN EMISSIONS ON A CONTINENTAL BASIS. 
In THE ULTIMATE MODEL, IT WILL BE POSSIBLE TO PREDICT 
THE ENVIRONMENTAL SIGNIFICANCE OF CHANGES IN THE MORE 
IMPORTANT SINGULAR SOURCES. 



396 



TERRESTRIAL INVESTIGATIONS CONSIST OF THE FOLLOWING 
ACTIVITIES: MAPPING OF SOIL AND VEGETATION SENSITIVITIES 
ON A PROVINCIAL SCALE. THE ESTABLISHMENT OF BASELINE 
SOIL AND VEGETATION DATA AND THE ESTABLISHMENT OF 
PERMANENT SAMPLE PLOTS ON A PROVINCIAL BASIS. IN 
ADDITION, LABORATORY STUDIES WHICH ARE USING SIMULATED 
ACID RAIN OF VARYING CONCENTRATIONS ARE UNDERWAY. ThIS 
ALLOWS THE COMPRESSION OF THE NATURALLY OCCURRING 
TIMEFRAME AND ASSISTS IN ELUCIDATING THE TEMPORAL 
ASPECT OF THIS PROBLEM AS IT RELATES TO IMPORTANT CROPS. 

A GREAT DEAL OF WORK IS CURRENTLY UNDERWAY. TO DEAL 
WITH THE ASPECTS OF MATERIAL DAMAGE, AESTHETICS IMPEDIMENT, 
AND HUMAN HEALTH EFFECTS FROM THIS PHENOMENON. ONTARIO 
HAS INTEGRATED, WHERE POSSIBLE AND APPROPRIATE, ITS 
ACTIVITIES TO A HIGH DEGREE WITH INDEPENDENT ACADEMIC 
STUDIES AND FEDERAL INVESTIGATIVE AGENCIES. 



397 



S QCIQ-ECQNQMIC ACTIVITIES 

SOCIO-ECONOMIC ACTIVITIES FORM AN INTEGRAL PART OF ThE 

Acidic Precipitation In Ontario Study. In the ultimate 
selection of policy recommendations^ it will be imperative 
to have detailed^ quantitative cost-benefit data on the 

IMPACT OF THIS PHENOMENON ON OnTARIO'S ECONOMY. In 
ORDER TO ASSIST IN THE ACQUISITION OF THE NECESSARY 
INFORMATION, THE ONTARIO MINISTRY OF THE ENVIRONMENT, 
ACTING AS THE LEAD AGENCY^ HAS INTEGRATED ACTIVITIES WITH 
THE FOLLOWING MINISTRIES: ThE MINISTRY OF NATURAL 

Resources, The Ministry of Industry and Tourism, The 
Ministry of Energy, The Hinistry of Agriculture and 
Food, and The Ministry of Treasury and Economics. 
These Ministries, together, have catalogued activities 

under the following GUIDELINES: 

1) ENUMERATION OF PHYSICAL EFFECTS IN ORDER TO 
ESTIMATE THEIR VALUE IN DOLLARSj 

2) DETERMINATION OF PUBLIC ATTITUDES AND WILLINGNESS 
TO PAY; 

3) DEVELOPMENT OF ABATEMENT COST FUNCTIONS FOR SO2 
AND NO^; 

4) INVESTIGATION OF INTERIM MITIGATIVE COSTS AND 
EFFECTIVENESS; 



398 



5) exploration of policy instruments and options for 
abatement. 

a great deal of activity has been underway during this 
fiscal year and contracts have been let for the following 
specific studies; 

Tourism and Recreation Study - this study is currently 

BEING CARRIED OUT BY CuRRIE^ CoOPERS AND LyBRAND LtD . 
and will GENERATE ESTIMATES OF THE IMPACTS OF ACID RAIN 

on tourism and recreation expenditures including the 
jobs dependent on that section; 

Amenity Value Survey Study - this study is being designed 
BY A.R.A. Consultants of Toronto and will more clearly 
discern and estimate values that people place on environmental 
and recreational resources which are vulnerable to acid 
RAIN. This survey is also expected to provide new data 

ON recreational activities and will BE CARRIED OUT 

during the summer of 1981j 

Financial Value Study - this study will focus on the 
actual potential effects on sectors in the economy 

which produce GOODS AND SERVICES FOR SALE AND FOR WHICH 
MARKET PRICES ARE GENERALLY AVAILABLE, COMMERCIAL 
FISHING^ CORROSION OF STRUCTURES AND MATERIALS^ EFFECTS 



399 



ON NATIVE FISHERIES^ REDUCED PRODUCTION IN FORESTRY AND 
AGRICULTURE, ARE AMONG THE FACTORS TO BE TAKEN INTO 

ACCOUNT. This study is presently to go to tender. 

In addition, an Ontario/Canada Task Force to study 
Sudbury pollution abatement options was announced by 
the Environment Minister on August 29, 1980. This Task 
Force is part of the Ontario control program for INCO 
Ltd., as announced on May 1, 1980 in the House by the 
Honourable Harry Parrott. The Task Force will make a 
complete independent assessment of the possible technologies 
to further reduce emissions in the Sudbury area. Its 
objective is to report on the environmental, economic 

AND SOCIAL consequences OF ALTERNATIVE ABATEMENT 

OPTIONS. The Task Force is composed of senior representatives 
FROM THE Ontario Ministries of the Environment and 
Natural Resources and the Federal Departments of Environment, 
and Energy, Mines and Resources. In addition, one 

PUBLIC representative HAS BEEN NOMINATED BY EACH OF 
THESE GOVERNMENT AGENCIES. 



400 



SUmARY 

Ontario scientists and managers have been leaders in 

THE area of recognition AND ACTIONS AS THEY RELATE TO 
THIS PHENOMENON. ACTIONS TAKEN BY THE MINISTRY OF ThE 

Environment to date include the announcement of a 
Regulation^ which is the toughest means available under 

CURRENT legislation, TO FURTHER REDUCE INCO'S EMISSIONS 
TO THE PRESENT LEVEL OF 2500 TONS/DAY AND WITH THE 
VIEW OF FURTHER REDUCTIONS TO 1950 TONS/dAY BY DECEMBER 

31, 1982. In addition, all other sources in Ontario 

ARE CURRENTLY UNDER CLOSER SCRUTINY. In PARTICULAR, 

Ontario Hydro is in the process of developing a management 

SCHEME to deal WITH ITS EMISSIONS ON A PROVINCIAL 

BASIS. These proposals will shortly be presented for 

GOVERNMENT REVIEW AND RECOMMENDATIONS AND ULTIMATELY 
action WILL BE FORTHCOMING. OtHER PROVINCIAL SOURCES 
ARE ALSO BEING CONSIDERED AND ANNOUNCEMENTS WILL FOLLOW 
DEALING WITH THESE SOURCES IN DUE COURSE. 

As A LARGE NUMBER OF SOURCES THAT AFFECT ONTARIO ARE 

OUTSIDE OF Ontario's jurisdiction, it will be necessary 

IN THE INTERIM TO DEVELOP MEANS OF PROTECTING THOSE 
AREAS OF THE ENVIRONMENT THAT ARE DEEMED MOST SENSITIVE 
AND ECONOMICALLY IMPORTANT. To THAT END, A MAJOR PROGRAM 
IS CURRENTLY BEING DEVELOPED TO EXPERIMENTALLY EXPLORE 



F^-i 1 -■in ^ -r — -i^^- i»|i.j«^»il 1 1^ Ji ' --TV- r-^.--.» - — ,,j-— — .t»>- ■KSvi - j^»i^f,j^., -. ■- ■* 



401 



MEANSv SUCH AS THE APPLICATION OF CALCIUM CARBONATE^ TO 
PARTICULARLY IMPORTANT AND SUSCEPTIBLE WATERWAYS IN ORDER 
TO PROTECT THEM, In ADDITION^ DATA AND EXPERIENCE HAS 

been and will continue to be accumulated from the 
Scandinavian and New York experiences with respect to 
application of chemicals and the fostering of more 

tolerant fish SPECIES. OtHER POSSIBILITIES FOR ALLEVIATING 

this phenomenon are also being explored. some of these 
include whole watershed re-vegetation^ and so on. 

The Ontario Ministry of the Environment^ together with 

OTHER ministries, HAS FOCUSSED A GREAT DEAL OF ATTENTION 

on this very complex phenomenon. no effort has been 
spared to explore the scientific, as well as the socio- 
economic aspects and a great deal of energy has been 
put into ensuring communication, cooperation and ultimate 
integration with other areas of investigation, including 
Federal studies. Ontario is well represented on all 

THE committees WHICH HAVE RESULTED FROM THE MEMORANDUM 

OF Intent signed between the Federal American and 
Canadian governments. 

In conclusion, as citizens of this province and country^ 
it falls upon us to take whatever means and measures 

ARE available TO HELP ALLEVIATE THIS PROBLEM. ThESE 
measures INCLUDE: 



402 



COMMUNICATING OUR CONCERN TO ELECTED REPRESENTATIVES^ 

BOTH Federally and Provincially; 

informing our fellow americans of their contribution 
to the problem and our unwillingness to let this 
situation continue; 

modifying our everyday activities to reduce our 
energy consumption and material wastage which 
ultimately affect emissions. 

Only through the mechanism of personal communication 

AND ultimate INDIVIDUAL INFLUENCE ON THE GOVERNMENTS IN 
BOTH COUNTRIES WILL STRONG CORRECTIVE ACTION BE 
TAKEN TO DEAL WITH THIS CONTEMPORARY^ VERY COMPLEX^ AND 
ENVIRONMENTALLY DEBILITATING PHENOMENON. 



BIBLIOGRAPHY 



1. Altshuller. a. P.J McBean. G. A.. Thf. LRTAP Prosi^m 
IN North America: A Prel iminary Overview. 
October. 1979. 



2, CoNROY. et.al.; M.O.E. Report, Extensive I^qnitoring 
OF Lakes in the Greater Su dbury Area. 197^-1976. 
1978. 



-"■ sir ;